Leuco triphenylmethane colorants as bluing agents in laundry care compositions

ABSTRACT

This application describes laundry care compositions that contain leuco colorants and their use in the laundering of textile articles. These types of colorants are provided in a stable, substantially colorless state and then may be transformed to an intense colored state upon exposure to certain physical or chemical changes such as, for example, exposure to oxygen, ion addition, exposure to light, and the like. The laundry care compositions containing the leuco colorants are designed to enhance the apparent or visually perceived whiteness of, or to impart a desired hue to, textile articles washed or otherwise treated with the laundry care composition.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims priority to and is a continuation of U.S. patentapplication Ser. No. 15/963,147, now U.S. Pat. No. 10,723,982, entitled“Leuco Triphenylmethane Colorants as Bluing Agents in Laundry CareCompositions,” which was filed on Apr. 26, 2018, which claims priorityto and is a divisional of U.S. patent application Ser. No. 15/145,865,now U.S. Pat. No. 9,982,221, entitled “Leuco Triphenylmethane Colorantsas Bluing Agents in Laundry Care Compositions,” which was filed on May4, 2016, which claims priority to U.S. Patent Application Ser. No.62/156,410, entitled “Leuco Triphenylmethane Colorants as Bluing Agentsin Laundry Care Compositions,” which was filed on May 4, 2015, all ofwhich are entirely incorporated by reference herein.

TECHNICAL FIELD

This application describes laundry care compositions that contain leucocolorants and their use in the laundering of textile articles. Thesetypes of colorants are provided in a stable, substantially colorlessstate and then may be transformed to an intense colored state uponexposure to certain physical or chemical changes such as, for example,exposure to oxygen, ion addition, exposure to light, and the like. Thelaundry care compositions containing the leuco colorants are designed toenhance the apparent or visually perceived whiteness of, or to impart adesired hue to, textile articles washed or otherwise treated with thelaundry care composition.

BACKGROUND

Leuco dyes are known in the prior art to exhibit a change from acolorless or slightly colored state to a colored state upon exposure tospecific chemical or physical triggers. The change in coloration thatoccurs is typically visually perceptible to the human eye. All existingcompounds have some absorbance in the visible light region (400-700 nm),and thus more or less have some color. In this invention, a dye isconsidered as a “leuco dye” if it did not render a significant color atits application concentration and conditions, but renders a significantcolor in its triggered form. The color change upon triggering stems fromthe change of the molar attenuation coefficient (also known as molarextinction coefficient, molar absorption coefficient, and/or molarabsorptivity in some literatures) of the leuco dye molecule in the400-700 nm range, preferably in the 500-650 nm range, and mostpreferably in the 530-620 nm range. The increase of the molarattenuation coefficient of a leuco dye before and after the triggeringshould be bigger than 50%, more preferably bigger than 200%, and mostpreferable bigger than 500%. In some cases the leuco compound can beused with other colorants, and other colorants may interfere theabsorbance of the leuco dye before and/or after triggering. In thiscase, it is best to measure leuco dye and its colored form separately ina solvent. The method of measuring molar attenuation coefficient of acompound is well-known. A description of the molar attenuationcoefficient (in the name of molar absorption coefficient) and itsmeasurement method can be found in Vogel's Textbook of quantitativechemical analysis, 5th edition, 1989, John Wiley and Sons. The chemicalor physical triggers that bring about the coloration change include, butare not limited to, oxidation, intramolecular ring opening, pH change,and exposure to heat and/or cold or light (e.g. UV light). For example,triphenylmethane (“TPM”) compounds, one class of leuco dyes, are usefulin applications such as photoimaging and typewritten ribbons wherebymicroencapsulated TPMs are brought into contact with an acid source andimages are generated when pressure or heat is applied. These dyes aredescribed, for example, in Chemistry and Applications of Leuco Dyes(edited by Ramaiah Muthyala, pp. xi-xiii; 151-152).

The use of polymeric colorants for coloring consumer products is wellknown in the prior art.

As one non-limiting example, the use of whitening agents, either opticalbrighteners or blueing agents, in textile applications is known. Astextile substrates age, their color tends to fade or yellow due toexposure to light, air, soil, and natural degradation of the fibers thatcomprise the substrates. Thus, the purpose of whitening agents isgenerally to visually brighten these textile substrates and counteractthe fading and yellowing of the substrates.

Previous attempts to add bluing agents to fabric care products have usedpreformed pigments or dyes such as azo dyes, triaminotriphenyl methanecompounds, triphenyl methane compounds and anthraquinone colorants. U.S.Pat. No. 4,137,243 to Farmer teaches polymeric anthraquinone-derivedcolorants which exhibit improved light and alkali fastness properties.Farmer also discloses that these colorants may be incorporated intodetergent compositions to provide coloration or blueing effect for thedetergent composition. These types of colorants must therefore be alkalifast, in order to withstand the alkaline conditions of the detergentcomposition. The colorants should also be water fugitive so as to notstain the textile articles washed with the colored detergentcomposition. However, Farmer does not disclose leuco colorants that havethe ability to transform from a colorless to a colored state uponexposure to certain physical or chemical changes.

U.S. Pat. No. 5,039,782 to Langer et al. discloses a copolymer whiteningagent that contains a fluorescent group and a hydrophilic group. Thewhitening agent is preferably 4,4′-bis(carbomethoxystilbene), and thehydrophilic group is preferably a mixture of polyethylene glycol andethylene glycol. The copolymer optionally contains a hydrophobic monomerportion, such as polyethylene terephthalate, in order to better adherethe polymer to a hydrophobic surface (like polyester fabric or soiledcotton fabric). The resulting copolymer provides dual functionality as awhitening agent and for providing soil release to fabrics. However, itis apparent from the test data provided in Table 3 of the reference thatthe copolymer fails to provide adequate whitening for soiled cottonfabrics without the addition of a second whitening agent (i.e.,Tinopal). Furthermore, Langer et al. fail to disclose leuco colorantsthat exhibit a reversible transformation from a colorless to a coloredstate.

U.S. Pat. No. 7,208,459 to Sadlowski et al. discloses the use of hueingdyes in laundry detergent compositions for combating the yellowing offabrics. The hueing dye is designed to avoid significant build up of thedye on fabric so that the fabric does not exhibit a bluish tint, forexample, after repeated exposure to the hueing dye present in laundrydetergent. The laundry detergent composition is comprised of asurfactant and a hueing dye. The surfactant may be anionic, nonionic,cationic, zwitterionic, and/or amphoteric in nature. The hueing dye ischaracterized by having a hueing efficiency of at least 10 and a washremoval value in the range of between 30% and 80%. Exemplary dyes whichexhibit these properties include certain categories of dyes that containblue or violet chromophores, such as triarylmethane dyes, basic dyes,anthraquinone dyes, and azo dyes. However, this reference fails todisclose the use of unsubstituted or leuco colorants as described by thepresent invention.

Thus, it is contemplated to be within the scope of the present inventionthat the leuco colorants described herein may be ideally suited for useas whitening agents. Many of the whitening agents that are commerciallyavailable exhibit a dark color, e.g. a dark blue color, when added to alaundry care composition, such as a laundry detergent, rinse aid, fabricsoftener, and the like. For instance, the triphenyl methane andthiazolium structures are positively charged colored species. Withcolored species such as these, the amount of color is visually apparentand may be an undesired shade for consumers. Powdered detergent systemstypically use colored speckles to reduce apparent color of the detergentby incorporation of color within the interior of a speckle or granule.Liquid products often incorporate opacity modifiers to reduce theapparent darkness of the product.

The need exists for an effective whitening agent that consumers can usewithout concern that the garments and other textile substrates will beirreversible stained with the laundry detergent composition thatcontains a whitening agent. Thus, the colorless leuco colorantsdescribed herein may be added to laundry care compositions without fearof staining, since these colorants are colorless when added to thelaundry machine and only exhibit color during the laundry cycle and/orupon exposure to ultraviolet light when the whitening effect isachieved.

The present invention offers advantages over U.S. Pat. Nos. 4,137,243and 5,039,782 and US Patent Application Publication No. 2005/0288206 asthis invention takes advantage of colorless compounds that can beconverted to colored compounds with the addition of certain physicaland/or chemical catalysts. Such compounds are useful for many consumerproducts, including, but not limited to, their use as whitening agentsin laundry care compositions. As whitening agents, the colored compoundsexhibit the desired wavelengths in the range of blue, red, violet,purple, or combinations thereof upon exposure to ultraviolet light (or,they absorb light to produce the same shades) in order to neutralize theyellowness of textile substrates and provide a brightening effect.

SUMMARY

This invention relates to a composition comprising: (a) at least onesurfactant and (b) at least one compound represented by Formula (I)below:

wherein X₁, X₂, X₃ and R₁ to R₁₂ groups are independently selected fromthe group consisting of halogens, hydrogen, a hydroxy group, a nitrogroup, alkyl groups, substituted alkyl groups, —S(O)₂OH, —S(O)₂O⁻[M⁺],—C(O)OR₁₃, —C(O)R₁₃, —C(O)NR₁₃R₁₄, —NC(O)OR₁₃, —NC(O)SR₁₃, —OR₁₃,—NR₁₃R₁₄, —S(O)₂R₁₃, S(O)₂NR₁₃R₁₄, and —P(O)₂R₁₃; M is a cation; R₁₃ andR₁₄ are independently selected from the group consisting of hydrogen,alkyl groups, substituted alkyl groups, aryl groups, substituted arylgroups, and R_(a); wherein R_(a) is selected from the group consistingof —R_(x)—O—R_(y)—R_(z) and —R_(y)—R_(z); R_(x) is selected from thegroup consisting of alkanediyl groups and arenediyl groups; R_(z) isselected from the group consisting of hydrogen, alkyl groups,substituted alkyl groups, acyl groups, and R_(b); R_(b) is a monovalentgroup conforming to a structure selected from the group consisting ofFormula I; and R_(y) is a divalent substituent selected from the groupconsisting of:

-   -   (i) divalent substituents comprising two or more divalent        repeating units independently selected from repeating units        conforming to the structure of Formula (C)

wherein R₁₀₁ and R₁₀₂ are independently selected from the groupconsisting of hydrogen, alkyl, hydroxyalkyl, aryl, alkoxyalkyl, andaryloxyalkyl;

-   -   (ii) divalent substituents conforming to the structure of        Formula (CX)

-   -   wherein R₁₁₁ and R₁₁₂ are independently selected from the group        consisting of hydrogen, hydroxyl, and C₁-C₁₀ alkyl, aa is an        integer from 1 to 12, and bb is an integer greater than or equal        to 1 (e.g., from 1 to 100);    -   (iii) divalent substituents conforming to the structure of        Formula (CXX)

wherein R₁₂₁ and R₁₂₂ are independently selected from the groupconsisting of hydrogen, hydroxyl, and C₁-C₁₀ alkyl, cc is an integerfrom 1 to 12, and dd is an integer greater than or equal to 1 (e.g.,from 1 to 100);

-   -   (iv) divalent substituents conforming to the structure of        Formula (CXXX)

wherein R₁₃₁, R₁₃₂ and R₁₃₃ are independently selected from alkyl andhydroxyalkyl, and ee is an integer greater than or equal to 1 (e.g.,from 1 to 100);

-   -   (v) divalent substituents conforming to the structure of Formula        (CXL)

wherein each R₁₄₁ is independently selected from the group consisting ofhydrogen and alkylamine groups, and ff is an integer greater than orequal to 1 (e.g., from 1 to 100);

-   -   (vi) divalent substituents conforming to the structure of        Formula (CL)

wherein gg is an integer greater than or equal to 1 (e.g., from 1 to100);

(vii) divalent substituents conforming to the structure of Formula (CLX)

wherein each R₁₆₁ is independently selected from the group consisting ofhydrogen and methyl, and hh is an integer greater than or equal to 1(e.g., from 1 to 100);

-   -   (viii) divalent substituents conforming to the structure of        Formula (CLXX)

wherein each R₁₇₁, R₁₇₂, and R₁₇₃ is independently selected from thegroup consisting of hydrogen and —CH₂CO₂H, and jj is an integer greaterthan or equal to 1 (e.g., from 1 to 100); and

-   -   (ix) divalent substituents comprising two or more substituents        selected from the group consisting of substituents conforming to        a structure of Formula (C), (CX), (CXX), (CXXX), (CXL), (CL),        (CLX), or (CLXX).

This invention also relates to a laundry care composition comprising:(a) at least one laundry care adjunct material and (b) at least oneleuco dye, wherein the leuco dye forms color upon exposure to anoxidation reaction and has a standard redox potential of greater thanzero volts at neutral pH.

This invention further relates to a laundry care composition comprising:(a) at least one laundry care adjunct material and (b) at least onecompound represented by Formula (I) below:

wherein X₁, X₂, X₃ and R₁ to R₁₂ groups are independently selected fromthe group consisting of halogens, hydrogen, a hydroxy group, a nitrogroup, alkyl groups, substituted alkyl groups, —S(O)₂OH, —S(O)₂O⁻[M⁺],—C(O)OR₁₃, —C(O)R₁₃, —C(O)NR₁₃R₁₄, —NC(O)OR₁₃, —NC(O)SR₁₃, —OR₁₃,—NR₁₃R₁₄, —S(O)₂R₁₃, S(O)₂NR₁₃R₁₄, and —P(O)₂R₁₃; M is a cation; R₁₃ andR₁₄ are independently selected from the group consisting of hydrogen,alkyl groups, substituted alkyl groups, aryl groups, substituted arylgroups, and R_(a); wherein R_(a) is selected from the group consistingof —R_(x)—O—R_(y)—R_(z) and —R_(y)—R_(z); R_(x) is selected from thegroup consisting of alkanediyl groups and arenediyl groups; R_(z) isselected from the group consisting of hydrogen, alkyl groups,substituted alkyl groups, acyl groups, and R_(b); R_(b) is a monovalentgroup conforming to a structure selected from the group consisting ofFormula I; and R_(y) is a divalent substituent selected from the groupconsisting of:

-   -   (i) divalent substituents comprising two or more divalent        repeating units independently selected from repeating units        conforming to the structure of Formula (C)

wherein R₁₀₁ and R₁₀₂ are independently selected from the groupconsisting of hydrogen, alkyl, hydroxyalkyl, aryl, alkoxyalkyl, andaryloxyalkyl;

-   -   (ii) divalent substituents conforming to the structure of        Formula (CX)

-   -   wherein R₁₁₁ and R₁₁₂ are independently selected from the group        consisting of hydrogen, hydroxyl, and C₁-C₁₀ alkyl, aa is an        integer from 1 to 12, and bb is an integer greater than or equal        to 1 (e.g., from 1 to 100);    -   (iii) divalent substituents conforming to the structure of        Formula (CXX)

wherein R₁₂₁ and R₁₂₂ are independently selected from the groupconsisting of hydrogen, hydroxyl, and C₁-C₁₀ alkyl, cc is an integerfrom 1 to 12, and dd is an integer greater than or equal to 1 (e.g.,from 1 to 100);

-   -   (iv) divalent substituents conforming to the structure of        Formula (CXXX)

wherein R₁₃₁, R₁₃₂, and R₁₃₃ are independently selected from alkyl andhydroxyalkyl, and ee is an integer greater than or equal to 1 (e.g.,from 1 to 100);

-   -   (v) divalent substituents conforming to the structure of Formula        (CXL)

wherein each R₁₄₁ is independently selected from the group consisting ofhydrogen and alkylamine groups, and ff is an integer greater than orequal to 1 (e.g., from 1 to 100);

-   -   (vi) divalent substituents conforming to the structure of        Formula (CL)

wherein gg is an integer greater than or equal to 1 (e.g., from 1 to100);

-   -   (vii) divalent substituents conforming to the structure of        Formula (CLX)

wherein each R₁₆₁ is independently selected from the group consisting ofhydrogen and methyl, and hh is an integer greater than or equal to 1(e.g., from 1 to 100);

-   -   (viii) divalent substituents conforming to the structure of        Formula (CLXX)

wherein each R₁₇₁, R₁₇₂, and R₁₇₃ is independently selected from thegroup consisting of hydrogen and —CH₂CO₂H, and jj is an integer greaterthan or equal to 1 (e.g., from 1 to 100); and

-   -   (ix) divalent substituents comprising two or more substituents        selected from the group consisting of substituents conforming to        a structure of Formula (C), (CX), (CXX), (CXXX), (CXL), (CL),        (CLX), or (CLXX).

This invention also relates to a polymeric leuco colorant represented byFormula (I) below:

wherein X₁, X₂, X₃ and R₁ to R₁₂ groups are independently selected fromthe group consisting of halogens, hydrogen, a hydroxy group, a nitrogroup, alkyl groups, substituted alkyl groups, —S(O)₂OH, —S(O)₂O⁻[M⁺],—C(O)OR₁₃, —C(O)R₁₃, —C(O)NR₁₃R₁₄, —NC(O)OR₁₃, —NC(O)SR₁₃, —OR₁₃,—NR₁₃R₁₄, —S(O)₂R₁₃, S(O)₂NR₁₃R₁₄, and —P(O)₂R₁₃; M is a cation; R₁₃ andR₁₄ are independently selected from the group consisting of hydrogen,alkyl groups, substituted alkyl groups, aryl groups, substituted arylgroups, and R_(a); wherein R_(a) is selected from the group consistingof —R_(x)—O—R_(y)—R_(z) and —R_(y)—R_(z); R_(x) is selected from thegroup consisting of alkanediyl groups and arenediyl groups; R_(z) isselected from the group consisting of hydrogen, alkyl groups,substituted alkyl groups, acyl groups, and R_(b); R_(b) is a monovalentgroup conforming to a structure selected from the group consisting ofFormula I; and R_(y) is a divalent substituent selected from the groupconsisting of:

-   -   (i) divalent substituents comprising two or more divalent        repeating units independently selected from repeating units        conforming to the structure of Formula (C)

wherein R₁₀₁ and R₁₀₂ are independently selected from the groupconsisting of hydrogen, alkyl, hydroxyalkyl, aryl, alkoxyalkyl, andaryloxyalkyl;

-   -   (ii) divalent substituents conforming to the structure of        Formula (CX)

-   -   wherein R₁₁₁ and R₁₁₂ are independently selected from the group        consisting of hydrogen, hydroxyl, and C₁-C₁₀ alkyl, aa is an        integer from 1 to 12, and bb is an integer greater than or equal        to 1 (e.g., from 1 to 100);    -   (iii) divalent substituents conforming to the structure of        Formula (CXX)

wherein R₁₂₁ and R₁₂₂ are independently selected from the groupconsisting of hydrogen, hydroxyl, and C₁-C₁₀ alkyl, cc is an integerfrom 1 to 12, and dd is an integer greater than or equal to 1 (e.g.,from 1 to 100);

-   -   (iv) divalent substituents conforming to the structure of        Formula (CXXX)

wherein R₁₃₁, R₁₃₂, and R₁₃₃ are independently selected from alkyl andhydroxyalkyl, and ee is an integer greater than or equal to 1 (e.g.,from 1 to 100);

-   -   (v) divalent substituents conforming to the structure of Formula        (CXL)

wherein each R₁₄₁ is independently selected from the group consisting ofhydrogen and alkylamine groups, and ff is an integer greater than orequal to 1 (e.g., from 1 to 100);

-   -   (vi) divalent substituents conforming to the structure of        Formula (CL)

wherein gg is an integer greater than or equal to 1 (e.g., from 1 to100);

-   -   (vii) divalent substituents conforming to the structure of        Formula (CLX)

wherein each R₁₆₁ is independently selected from the group consisting ofhydrogen and methyl, and hh is an integer greater than or equal to 1(e.g., from 1 to 100);

-   -   (viii) divalent substituents conforming to the structure of        Formula (CLXX)

wherein each R₁₇₁, R₁₇₂, and R₁₇₃ is independently selected from thegroup consisting of hydrogen and —CH₂CO₂H, and jj is an integer greaterthan or equal to 1 (e.g., from 1 to 100); and

-   -   (ix) divalent substituents comprising two or more substituents        selected from the group consisting of substituents conforming to        a structure of Formula (C), (CX), (CXX), (CXXX), (CXL), (CL),        (CLX), or (CLXX);        wherein at least one of X₁, X₂, X₃, and R₁-R₁₂ includes at least        one R_(a) group.

DETAILED DESCRIPTION

All patents, published patent applications, and any other publicationsmentioned in this patent application are herein incorporated entirely byreference.

Definitions

As used herein, the term “alkoxy” is intended to include C₁-C₈ alkoxyand alkoxy derivatives of polyols having repeating units such asbutylene oxide, glycidol oxide, ethylene oxide or propylene oxide.

As used herein, the terms “polyalkyleneoxy” and “polyoxyalkylene,” asused interchangeably herein, generally refer to molecular structurescontaining the following repeating units: —CH₂CH₂O—, —CH₂CH₂CH₂O—,—CH₂CH₂CH₂CH₂O—, —CH₂CH(CH₃)O—, —CH₂CH₂CH(CH₃)O—, and any combinationsthereof. Furthermore, the polyoxyalkylene constituent may be selectedfrom the group consisting of one or more monomers selected from a C₂₋₂₀alkyleneoxy group, a glycidol group, a glycidyl group, or mixturesthereof.

As used herein, unless otherwise specified, the terms “alkyl” and “alkylcapped” are intended to include C₁-C₁₈ alkyl groups, and in one aspect,C₁-C₆ alkyl groups.

As used herein, unless otherwise specified, the term “aryl” is intendedto include C₃-C₁₂ aryl groups.

As used herein, unless otherwise specified, the term “arylalkyl” isintended to include C₁-C₁₈ alkyl groups and, in one aspect, C₁-C₆ alkylgroups.

The terms “ethylene oxide,” “propylene oxide” and “butylene oxide” maybe shown herein by their typical designation of “EO,” “PO” and “BO,”respectively.

As used herein, the term “laundry care composition” includes, unlessotherwise indicated, granular, powder, liquid, gel, paste, unit dose,bar form and/or flake type washing agents and/or fabric treatmentcompositions, including but not limited to products for launderingfabrics, fabric softening compositions, fabric enhancing compositions,fabric freshening compositions, and other products for the care andmaintenance of fabrics, and combinations thereof. Such compositions maybe pre-treatment compositions for use prior to a washing step or may berinse added compositions, as well as cleaning auxiliaries, such asbleach additives and/or “stain-stick” or pre-treat compositions orsubstrate-laden products such as dryer added sheets.

As used herein, the term “detergent composition” is a sub-set of laundrycare composition and includes cleaning compositions including but notlimited to products for laundering fabrics. Such compositions may bepre-treatment composition for use prior to a washing step or may berinse added compositions, as well as cleaning auxiliaries, such asbleach additives and “stain-stick” or pre-treat types.

As used herein, “cellulosic substrates” are intended to include anysubstrate which comprises at least a majority by weight of cellulose.Cellulose may be found in wood, cotton, linen, jute, and hemp.Cellulosic substrates may be in the form of powders, fibers, pulp andarticles formed from powders, fibers and pulp. Cellulosic fibers,include, without limitation, cotton, rayon (regenerated cellulose),acetate (cellulose acetate), triacetate (cellulose triacetate), andmixtures thereof. Articles formed from cellulosic fibers include textilearticles such as fabrics. Articles formed from pulp include paper.

As used herein, the term “maximum extinction coefficient” is intended todescribe the molar extinction coefficient at the wavelength of maximumabsorption (also referred to herein as the maximum wavelength), in therange of 400 nanometers to 750 nanometers.

As used herein “average molecular weight” of the leuco colorant isreported as an average molecular weight, as determined by its molecularweight distribution: as a consequence of their manufacturing process,the leuco colorants disclosed herein may contain a distribution ofrepeating units in their polymeric moiety.

The test methods disclosed in the Test Methods Section of the presentapplication should be used to determine the respective values of theparameters of Applicants' inventions.

As used herein, articles such as “a” and “an” when used in a claim, areunderstood to mean one or more of what is claimed or described.

As used herein, the terms “include/s” and “including” are meant to benon-limiting.

As used herein, the term “solid” includes granular, powder, bar andtablet product forms.

As used herein, the term “fluid” includes liquid, gel, paste and gasproduct forms.

Unless otherwise noted, all component or composition levels are inreference to the active portion of that component or composition, andare exclusive of impurities, for example, residual solvents orby-products, which may be present in commercially available sources ofsuch components or compositions.

All percentages and ratios are calculated by weight unless otherwiseindicated. All percentages and ratios are calculated based on the totalcomposition unless otherwise indicated.

The present invention relates to a class of leuco colorants that may beuseful for use in laundry care compositions, such as liquid laundrydetergent, to provide a blue hue to whiten textile substrates. Leucocolorants are compounds that are essentially colorless or only lightlycolored but are capable of developing an intense color upon activation.One advantage of using leuco compounds in laundry care compositions isthat such compounds, being colorless until activated, allow the laundrycare composition to exhibit its own color. The leuco colorant generallydoes not alter the primary color of the laundry care composition. Thus,manufacturers of such compositions can formulate a color that is mostattractive to consumers without concern for added ingredients, such asbluing agents, affecting the final color value of the composition.

Another advantage of leuco colorants is found in their structure. Leucocolorants typically provide less conjugated chemical structures andlarger HOMO-LUMO energy gaps. Therefore, leuco colorants tend to be morestable in the high pH environments of laundry care compositions.

It is also important to note that the polymeric form of the leuco dyesof the present invention exhibit selective fugitivity. In other words,they are designed for selective staining or non-staining characteristicsin their polymeric form and to also demonstrate the color changetransformation when exposed to certain physical or chemical changes.

Leuco dyes include the following classes of compounds: spirobenzopyrans,spironaphthooxazines, spirothiopyrans, leuco quinones, leucoanthraquinones, thiazine leuco colorants, oxazine leuco colorants,phenanzine leuco colorants, phthalide based leucos, tetrazolium basedleucos, triphenylmethanes, triarylmethanes, fluorans, and leucodiarylmethanes. A preferred class of leuco compounds includestriphenylmethane colorants. It is contemplated that the leuco colorantsof the present invention may or may not be encapsulated for usedepending on the desired end use of the product containing thecolorants.

Triphenylmethane (“TPM”) structures of the N,N disubstituted diamino andtriaminophenyl methane compounds produce bluish shades that aredecolorized by complexation or reaction with strong ions. Examples ofsuitable ions include, for example, hydroxyl ions, cyanide ions, cyanateions, and mixtures thereof. The highly alkaline environment needed toproduce hydroxyl ions is typically not suitable for products in theneutral to acidic pH range. The cyano product is colorless until exposedto ultraviolet (“UV”) light. Upon exposure to UV light, the originalblue color is generated and the bluing effect is observed. A laundrycare composition may be colored to a consumer pleasing level, and theamount of bluing on the treated textile substrate may be adjusted to themost desirable level. It is also noted that at least some of thecolorants of the present invention possess the ability to provide alatent color that is stable to conditions that degrade the coloredspecies. For example, the triphenyl acetonitrile leuco colorants arestable to strong base and heat while the colored versions degrade. Theleuco form of methylene blue is stable to strong reducing agents whilemost classes of colorants are irreversibly decolorized.

In another embodiment, one approach may be to use colorless bluecolorant precursors that are sensitive to oxygen. For example, methyleneblue can be reduced to its colorless leuco form. For a practicalapplication, a small amount of reducing agent can be added at thebottling stage to convert the colorant to its colorless form in theclosed bottle. Suitable reducing agents include hydrosulfite, reducingsugars, and the like, and mixtures thereof. Thiazolium or othermericyanine dyes may be converted to colorless forms by ion addition.

Finally, blends of conventional optical brighteners or bluing agents andcolorless bluing agent precursors can be used to provide whiteningeffects, whether the effect is achieved immediately upon application orwhether it is formulated to provide an increased bluing effect over timeor on color generating exposure.

Examples of suitable polymeric constituents that comprise the leucopolymeric colorants include polyoxyalkylene chains having multiplerepeating units. Preferably the polymeric constituents includepolyoxyalkylene chains having from 2 to about 100 repeating units, andmore preferably from 2 to about 20 or even from about 4 to about 10repeating units. Non-limiting examples of polyoxyalkylene chains includeethylene oxide, propylene oxide, glycidol oxide, butylene oxide andmixtures thereof.

The leuco colorant of the present invention may be characterized by thefollowing structure:

wherein X₁, X₂, X₃ and R₁ to R₁₂ groups are independently selected fromthe group consisting of halogens, hydrogen, a hydroxy group, a nitrogroup, alkyl groups, substituted alkyl groups, —S(O)₂OH, —S(O)₂O⁻[M⁺],—C(O)OR₁₃, —C(O)R₁₃, —C(O)NR₁₃R₁₄, —NC(O)OR₁₃, —NC(O)SR₁₃, —OR₁₃,—NR₁₃R₁₄, —S(O)₂R₁₃, S(O)₂NR₁₃R₁₄, and —P(O)₂R₁₃; M is a cation; R₁₃ andR₁₄ are independently selected from the group consisting of hydrogen,alkyl groups, substituted alkyl groups, aryl groups, substituted arylgroups, and R_(a); wherein R_(a) is selected from the group consistingof —R_(x)—O—R_(y)—R_(z) and —R_(y)—R_(z); R_(x) is selected from thegroup consisting of alkanediyl groups and arenediyl groups; R_(z) isselected from the group consisting of hydrogen, alkyl groups,substituted alkyl groups, acyl groups, and R_(b); R_(b) is a monovalentgroup conforming to a structure selected from the group consisting ofFormula I; and R_(y) is a divalent substituent selected from the groupconsisting of:

-   -   (i) divalent substituents comprising two or more divalent        repeating units independently selected from repeating units        conforming to the structure of Formula (C)

wherein R₁₀₁ and R₁₀₂ are independently selected from the groupconsisting of hydrogen, alkyl, hydroxyalkyl, aryl, alkoxyalkyl, andaryloxyalkyl;

-   -   (ii) divalent substituents conforming to the structure of        Formula (CX)

-   -   wherein R₁₁₁ and R₁₁₂ are independently selected from the group        consisting of hydrogen, hydroxyl, and C₁-C₁₀ alkyl, aa is an        integer from 1 to 12, and bb is an integer greater than or equal        to 1 (e.g., from 1 to 100);    -   (iii) divalent substituents conforming to the structure of        Formula (CXX)

wherein R₁₂₁ and R₁₂₂ are independently selected from the groupconsisting of hydrogen, hydroxyl, and C₁-C₁₀ alkyl, cc is an integerfrom 1 to 12, and dd is an integer greater than or equal to 1 (e.g.,from 1 to 100);

-   -   (iv) divalent substituents conforming to the structure of        Formula (CXXX)

wherein R₁₃₁, R₁₃₂, and R₁₃₃ are independently selected from alkyl andhydroxyalkyl, and ee is an integer greater than or equal to 1 (e.g.,from 1 to 100);

-   -   (v) divalent substituents conforming to the structure of Formula        (CXL)

wherein each R₁₄₁ is independently selected from the group consisting ofhydrogen and alkylamine groups, and ff is an integer greater than orequal to 1 (e.g., from 1 to 100);

-   -   (vi) divalent substituents conforming to the structure of        Formula (CL)

wherein gg is an integer greater than or equal to 1 (e.g., from 1 to100);

-   -   (vii) divalent substituents conforming to the structure of        Formula (CLX)

wherein each R₁₆₁ is independently selected from the group consisting ofhydrogen and methyl, and hh is an integer greater than or equal to 1(e.g., from 1 to 100);

-   -   (viii) divalent substituents conforming to the structure of        Formula (CLXX)

wherein each R₁₇₁, R₁₇₂, and R₁₇₃ is independently selected from thegroup consisting of hydrogen and —CH₂CO₂H, and jj is an integer greaterthan or equal to 1 (e.g., from 1 to 100); and

-   -   (ix) divalent substituents comprising two or more substituents        selected from the group consisting of substituents conforming to        a structure of Formula (C), (CX), (CXX), (CXXX), (CXL), (CL),        (CLX), or (CLXX).

In one aspect of the invention, the sum of ff, gg, and hh in all theX₁-X₃ and R₁-R₁₂ group is from 2 to 40. In another aspect of theinvention, the sum of ff, gg, and hh in all the X₁-X₃ and R₁-R₁₂ groupis from 2 to 20.

The leuco dyes which are useful in this invention are also those thatform a colored dye when subjected to an oxidation reaction. While someof these leuco dyes are well known in the art (e.g., The Theory of thePhotographic Process, 3rd Ed., Mees and James, pp. 283-4, 390-1,Macmillion Co., N.Y.; and Light-Sensitive Systems, Kosar, pp. 367,370-380, 406 (1965) Wiley and Sons, Inc., N.Y.), only those leuco dyesthat are stable to maintain its leuco form during storage are suitablefor this invention. Typically, one way to quantify whether a substanceis easy to be oxidized is to use the oxidation-reduction potential orredox potential. Redox potential is measured in volts or millivolts. Themore positive potential means the greater tendency for oxidized form ofthe specie to be reduced, and the less tendency for the reduced form tobe oxidized. To prevent premature color formation, it may be preferableto use leuco dyes that have a standard redox potential in aqueoussolution at neutral pH of greater than zero volts, or of greater than orequal to 0.2 volts, or of greater than or equal to 0.4 volts. Forexample, the redox potential of methylene blue has been reported to beabout zero volt at neutral pH. Applicants' have found that methyleneblue forms color during storage, which is an undesirable attribute ofthe present invention. The measurement of oxidation potentials is wellknown to the ordinarily skilled artisan. One of the many methodsutilized is cyclic voltammetry as described in textbooks (e.g.Electrochemistry for Chemists, 2^(nd) Edition, John Wiley & Sons, N.Y.,1995).

Suitable leuco colorants are set forth in Table 1A below. Thecorresponding chemical names, as determined by Chem Doodle softwareVersion 6.0 available from iChemLabs™, Cambridge, Mass., U.S.A., forsuch colorants are respectively provided in Table 1B below.

TABLE 1A Structures for Leuco Colorants Examples Structure of Leucotriphenylmethane (TPM) colorant EX 1

EX 2

EX 3

EX 4

EX 5

EX 6

EX 7

EX 8

EX 9

EX 10

EX 11

EX 12

EX 13

EX 14

TABLE 1B Chemical Names for Structures Provided in Table 1A ExampleIUPAC Name EX1p-{Bis[p-(dimethylamino)phenyl]methyl}(dimethylamino)benzene EX22-[2-(2-{[2-(2-Hydroxyethoxy)ethyl](p-{[p-(dimethylamino)phenyl][p-({2-[2-(2-hydroxyethoxy)ethoxy]ethyl}[2-(2-hydroxyethoxy)ethyl]amino)phenyl]methyl}phenyl)amino}ethoxy)ethoxy]ethanolEX32-(2-{2-[2-(2-{[2-(2-{2-[2-(2-Hydroxyethoxy)ethoxy]ethoxy}ethoxy)ethyl]{p-[(p-{bis[2-(2-{2-[2-(2-hydroxyethoxy)ethoxy]ethoxy}ethoxy)ethyl]amino}phenyl)[p-(dimethylamino)phenyl]methyl]phenyl}amino}ethoxy)ethoxy]ethoxy}ethoxy)ethanolEX41-(2-{2-[2-(2-{[2-(2-{2-[2-(2-Hydroxypropoxy)propoxy]propoxy}ethoxy)ethyl](p-{[p-(dimethylamino)phenyl](p-{[2-(2-{2-[2-(2-hydroxypropoxy)propoxy]ethoxy}ethoxy)ethyl][2-(2-{2-[2-(2-hydroxypropoxy)propoxy]propoxy}ethoxy)ethyl]amino}phenyl)methyl}phenyl)amino}ethoxy)ethoxy]ethoxy}-1-methylethoxy)-2-propanol EX51-(2-{2-[2-(2-{[2-(2-{2-[2-(2-Hydroxypropoxy)propoxy]ethoxy}ethoxy)ethyl]{p-[(p-{bis[2-(2-{2-[2-(2-hydroxypropoxy)propoxy]propoxy}ethoxy)ethyl]amino}phenyl)[p-(dimethylamino)phenyl]methyl]phenyl}amino}ethoxy)ethoxy]ethoxy}-1-methylethoxy)-2-propanol EX62-[(2-Hydroxyethyl)[p-({p-[bis(2-hydroxyethyl)amino]phenyl}[p-(dimethylamino)phenyl]methyl)phenyl]amino]ethanol EX71-(2-{[2-(2-Hydroxypropoxy)ethyl]{p-[(p-{bis[2-(2-hydroxypropoxy)ethyl]amino}phenyl)[p-(dimethylamino)phenyl]methyl]phenyl}amino}ethoxy)-2-propanol EX81-[2-(2-{2-[(2-{2-[2-(2-Hydroxypropoxy)propoxy]propoxy}propyl)[p-({p-[bis(2-{2-[2-(2-hydroxypropoxy)propoxy]propoxy}propyl)amino]phenyl}[p-(dimethylamino)phenyl]methyl)phenyl]amino]-1-methylethoxy}-1-methylethoxy)-1-methylethoxy]-2-propanol EX9p-{Bis[p-(methylamino)phenyl]methyl}(dimethylamino)benzene EX10p-{Bis[p-(methylamino)phenyl]methyl}(dimethylamino)benzene EX11p-[Bis(p-aminophenyl)methyl]benzenamine EX121-(2-{[2-(2-Hydroxypropoxy)propyl]{p-[(p-{bis[2-(2-hydroxypropoxy)propyl]amino}phenyl)[p-(dimethylamino)phenyl]methyl]phenyl}amino}-1-methylethoxy)-2-propanolEX13 1-{2-[2-({2-[2-(2-Hydroxypropoxy)propoxy]ethyl}(p-{[p-(bis{2-[2-(2-hydroxypropoxy)propoxy]ethyl}amino)phenyl][p-(dimethylamino)phenyl]methyl}phenyl)amino)ethoxy]-1-methylethoxy}-2-propanolEX141-(2-{2-[2-(2-{[2-(2-{2-[2-(2-Hydroxypropoxy)propoxy]propoxy}propoxy)ethyl]{p-[(p-{bis[2-(2-{2-[2-(2-hydroxypropoxy)propoxy]propoxy}propoxy)ethyl]amino}phenyl)[p-(dimethylamino)phenyl]methyl]phenyl}amino}ethoxy)-1-methylethoxy]-1-methylethoxy}-1-methylethoxy)-2-propanol

The Examples provided in Tables 1A and 1B are typically transformed fromtheir colorless to colored state by oxidation. For example, Examples1-14 can generate color upon exposure to an oxidation agent, such asoxygen, air and/or bleach.

There are multiple polymerization methods capable of preparing polymerchains attached to the leuco triphenylmethane colorants. Thepolymerization methods can be found in textbooks such as Principles ofPolymerization, third edition, John Wiley & Sons, 1991, by George Odian.Typical polymerization methods, such as step polymerization and chainpolymerization, all generate a distribution of the molecules withdifferent degrees of polymerization. The actual polymerization reactionis rather complicated and can be nearly impossible to predict the exactdistribution of the polymers nor to prepare a polymer to an exactdistribution, including a real mono-distributed polymer. With somesimplification, mathematical models have been developed as shown below:

-   -   1) Chain polymerization with disproportionate termination and/or        chain transfer to a monomeric molecule:        N _(i)=(1−p)×p ^((i−2))

N_(i) here is the mole fraction of the polymers containing i repeatunits, i.e., degree of polymerization of i, p is the possibility of thechain propagation, which can be calculated from the ratio of thereaction rate or polymer propagation (R_(p)), transfer (R_(tr)), andtermination (R_(t)):

$p = \frac{Rp}{{Rp} + {{Rt}\;\gamma} + {Rt}}$

The number average degree of polymerization will be:

$\overset{\_}{X_{n}} = \frac{1}{1\mspace{14mu} p}$

In this case, for a polymer chain with average about 10 repeating units(monomer), p will be 0.9. Then the mole fraction of the polymer chainswith only 1 repeat units will be about: (1−0.9)×1=0.1. That means therewill be about 10% “polymers” with only one repeat unit in thisdistribution.

-   -   2) Chain polymerization with coupling termination:        N _(i)=(i−1)×(1−p)² ×p ^((i−2))    -   N_(i) here is the mole fraction of the polymers containing i        repeat units, i.e., degree of polymerization of i, p is the        possibility of the chain propagation, which can be calculated        from the ratio of the reaction rate or polymer propagation        (R_(p)) and termination (R_(t)):

$p = \frac{Rp}{ {Rp}\; \middle| \;{Rt} }$

The number average degree of polymerization will be:

$\overset{\_}{X_{n}} = \frac{2}{1 - p}$

In this case, for a polymer chain with average about 10 repeating units(monomer), p will be 0.8. Then the mole fraction of the polymer chainswith only 2 repeat units will be about: 1×(1−0.8)²×1=0.04. That meansthere will be about 4% “polymers” with only 2 repeat units in thisdistribution.

-   -   3) Linear Step polymerization:    -   For a typical step polymerization with equal mole of A₂ and B₂        monomers yielding a linear polymer, then the mole fraction of        the polymer with degree of polymerization of i is:        N _(i)=(1−p)×p ^((i−1))    -   Here p is the possibility of the chain propagation, which is        also the conversion of the reaction.

The number average degree of polymerization will be:

$\overset{\_}{X_{n}} = \begin{matrix}1 \\{1 - p}\end{matrix}$

In this case, for a polymer chain with average about 10 repeating units(monomer), p will be 0.9. Then the mole fraction of the polymer chainswith only 2 repeat units will be about: (1−0.9)×0.9⁰=0.1. That meansthere will be about 10% “polymers” with only one repeat units in thisdistribution.

-   -   4) Living polymerization:    -   For living polymerization, which meaning the polymerization does        not have termination or transfer reaction, one can typically        generate a much more controllable molecular weight distribution.        For this reason, it is also referred to as “controlled        polymerization”, and the polymer is considered as “narrow        distributed” or even “mono-distributed.” However, this        polymerization still produces polymers with a distribution,        which follows Poisson distribution. The mole fraction of the        polymer with degree of polymerization of i is:

$N_{i} - {\frac{\lambda^{i}}{i!} \times e^{- \lambda}}$

Here λ is mean of the distribution, which is also the number averagedegree of polymerization.

In this case, for a polymer chain with average about 10 repeating units(monomer), λ

will be 10. Then the mole fraction of the polymer chains with only onerepeat unit will be about: 10×e⁻¹⁰≈0.0005. That means there will beabout 0.05% “polymers” with only one repeat units in this distribution.

The above four cases are based on mathematical models withsimplification. All the above models assumes the reactivity throughoutthe polymerization are the same, there is no diffusion limitation duringthe polymerization, and the reaction rates do not change as the startingmaterials are consumed. The real case will be much more complicated. Inthe case of copolymerization, reactivity of different monomers can bevery different. As a result, the polymer distribution can be bimodal andsometimes forms some “blocky” structures also known as block copolymers.

The leuco colorants of the present invention may be incorporated for useas whitening agents into a laundry care composition. Laundry carecompositions include, but are not limited to, laundry detergents andfabric care compositions such as, for example, liquid and/or powderlaundry detergent formulations and rinse added fabric softening (RAFS)compositions. Such compositions comprise one or more of said whiteningagents and a laundry care ingredient. The whitening agent may be presentin the laundry care composition in an amount from about 0.0001% to about10% by weight of the composition, more preferably from about 0.0001% toabout 5% by weight of the composition, and even more preferably fromabout 0.0001% to about 1% by weight of the composition.

The laundry care compositions, including laundry detergents, may be insolid or liquid form, including a gel form. The laundry detergentcomposition comprises a surfactant in an amount sufficient to providedesired cleaning properties. The laundry detergent composition comprisesa surfactant in an amount sufficient to provide desired cleaningproperties. In one embodiment, the laundry detergent compositioncomprises, by weight, from about 5% to about 90% of the surfactant, andmore specifically from about 5% to about 70% of the surfactant, and evenmore specifically from about 5% to about 40%. The surfactant maycomprise anionic, nonionic, cationic, zwitterionic and/or amphotericsurfactants. In a more specific embodiment, the detergent compositioncomprises anionic surfactant, nonionic surfactant, or mixtures thereof.

The leuco colorant may be incorporated into the composition in the formof a mixture of reaction products formed by the organic synthesis routeused: such a reaction mixture will typically comprise a mixture of thedyes of formula (I) and often, in addition, reaction products of sidereactions and/or minor amounts of unreacted starting materials. Althoughit may be preferred to remove impurities, it may not be necessary, sothe mixture of reaction products may be used directly in a compositionaccording to the invention.

Typically the leuco colorant of the present invention will be present inthe composition in an amount from 0.00001 to 5 wt % of the composition,more usually in an amount from 0.0001 to 1 wt % or to 0.5 wt % of thecomposition.

As a result of the leuco colorant synthesis process, chemical impuritiesand/or intermediates may be formed. One type of impurity that may bepresent is the residual starting material and/or reagents for thereaction. Another source of potential impurities and/or intermediates isrecognized as an oxidized version of the leuco colorants. A small amountof the leuco colorant may be oxidized when contacted with air or oxygento form colored triphenylmethane (TPM) dyes. The colored TPM dyes canfurther react with other ingredients in the product and/or the detergentto form other molecules. One example discussed in the literature is theTPM carbinol formed by the reaction of TPM dyes with hydroxyl anion(Turgeon, J. D., and LaMer, V. K., J. Amer. Chem. Soc., 74, 5988, 1952).The oxidized TPM can also react with other anions to form other leucocolorants. The other anions includes but not limited to OH⁻, CN⁻, HCO⁻,Br, HSO₄ ⁻, CO₃ ²⁻, citrate, Cl⁻. H₂PO₄ ⁻, F⁻, NO₃ ⁻, NO₂ ⁻, PO₄ ³⁻,HPO₄ ²⁻, SO₄ ²⁻, SO₃ ²⁻, SCN⁻, NCO⁻, HS⁻, S²⁻, alkoxylate, amide anion,oxalate, carboxylate, and etc.

An additional source of possible impurities is the side product of thereactions. Some typical side products of the reactions taught in thisinvention are Michler's hydrol and Michler's ketone. Michler's hydrolcan further eliminate the center hydroxyl group and form a coloredcation (see chemical structures below). However, the side products willdepend on the specific synthetic route of the target TPM molecules.Other synthetic routes, such as reduction of oxidized TPM, may havedifferent intermediates. The common synthetic route for TPM molecules,as well as the intermediate during each route, can be found in thechapter of Triphenylmethane and Related Dyes in Kirk-Othmer Encyclopediaof Chemical Technology by John Wiley & Sons.

Another source for the impurities would be the degradation product ofthe leuco TPM and the corresponding colored TPM. By biodegradation, TPMcan form Michler's ketone, aromatic aldehyde, and substituted orunsubstituted phenol compounds (Journal of Environmental Sciences 2011,23(8) 1384-1393). The Michler's ketone and substituted or unsubstitutedphenol compounds can also form during the TPM degradation in thepresence of oxidant and light (Chemical Review, 1993, 93, 381-433).Under some oxidation conditions, the TPM can also form some benzidineand diquinoid structures (J. Am. Chem. Soc., 1964, 86 (9), pp1666-1671). The TPM can also lose some of its substitution groups toform a different TPM molecule. In the case of crystal violet, it canlose its methyl group under light to form a series demethylated productsfrom methyl violet 6B, methyl violet 2B, to pararosaniline. It can alsolose its amino group to form diamond green structure and then toMichler's ketone (Journal of Physics: Conference Series 231 (2010)012011).

The impurities, such as the oxidized TPM, Michler's hydrol cation, TPMcarbinol, and Michler's hydrol can be intentionally added orunintentionally included to the composition with the leuco dye. Whenunintentionally included as the impurity of the leuco dye, they shouldbe less than 20 wt % of the leuco colorant, preferably less than 10 wt%, and most preferably less than 5 wt %. The effects of these compoundswith leuco dye included but not limited to 1) additional hueing effectbeside those the leuco TPM taught in this application, and 2) aestheticeffect. The colored impurities can be used to render the compositionwith a more desired color. It can be used with other aesthetic dyeand/or pigment to achieve more desirable effect. Another aestheticeffect is to “neutralize” the yellowish tint associated with thecomposition. With the small amount of oxidized TPM added with leuco TPMof this invention intentionally or unintentionally can render thecomposition a subtle blue hue. The subtle blue hue will balance theinherent yellowish color of the composition and make it brighter and/orwhiter in consumers' perception. Use of leuco dye in this applicationhave additional advantages. As leuco dye slowly develops, it can“neutralize” more and more yellowish color formed with time so that aprolonged whitening effect can be achieved that leads to aestheticallymore appealing base.

Several of these impurities and/or intermediates are shown below:

An exemplary oxidized TPM dye:

An exemplary TPM carbinol:

An exemplary Michler's hydrol and Michler's hydrol cation:

An exemplary Michler's ketone:

While several exemplary routes are disclosed for synthesizing the leucocolorants of the present invention, the invention should not be limitedto only these examples and synthetic routes. Additional startingmaterials and/or reagents for different synthetic routes and/ordifferent leuco colorants that are not exemplified herein are alsocontemplated to be covered by this invention.

The compositions of the present invention typically comprises, inaddition to the leuco colorant, one or more laundry care adjunctmaterials.

Another class of ingredients in the leuco colorants product is thediluent and/or solvent. The purpose of the diluent and/or solvent isoften but not limited to improving fluidity and/or reducing theviscosity of the leuco colorant. Although water is often the preferreddiluent and/or solvent given its low cost and non-toxicity, othersolvent may also be used as well. The preferred solvent is one havinglow cost and low hazards. Examples of suitable solvents include, but arenot limited to, ethylene glycol, propylene glycol, glycerin, alkoxylatedpolymers such as polyethylene glycol, polypropylene glycol, copolymersof ethylene oxide and propylene oxide, Tween 20®, Tween 40®, Tween 80®,and the like, and combinations thereof. Among the polymers, the ethyleneoxide and propylene oxide copolymers may be preferred. These polymersoften feature a cloud point with water, which can help the productseparated from the water to remove the undesirable water solubleimpurities. Examples of ethylene oxide and propylene oxide copolymersinclude but not limited to the PLURONIC series polymers by BASF andTERGITOL™ series polymer and by Dow. When the leuco colorant product isincorporated into the composite materials, these polymers may also actas the non-ionic surfactant.

Laundry Care Adjunct Materials

Suitable adjuncts may be, for example to assist or enhance cleaningperformance, for treatment of the substrate to be cleaned, for exampleby softening or freshening, or to modify the aesthetics of thecomposition as is the case with perfumes, colorants, non-fabric-shadingdyes or the like. Suitable adjunct materials include, but are notlimited to, surfactants, builders, chelating agents, dye transferinhibiting agents, dispersants, enzymes, and enzyme stabilizers,catalytic materials, bleach activators, hydrogen peroxide, sources ofhydrogen peroxide, preformed peracids, polymeric dispersing agents, claysoil removal/anti-redeposition agents, brighteners, suds suppressors,dyes, hueing dyes, perfumes, perfume delivery systems, structureelasticizing agents, fabric softeners, carriers, hydrotropes, processingaids, solvents, additional dyes and/or pigments, some of which arediscussed in more detail below. In addition to the disclosure below,suitable examples of such other adjuncts and levels of use are found inU.S. Pat. Nos. 5,576,282, 6,306,812 B1 and 6,326,348 B1 that areincorporated by reference.

Additional Fabric Hueing Agents.

The composition may comprise one or more additional fabric hueingagents. Suitable fabric hueing agents include dyes, dye-clay conjugates,and pigments. Suitable dyes include those that deposit more onto cottontextiles compared to deposition onto synthetic textiles such aspolyester and/or nylon. Further suitable dyes include those that depositmore onto synthetic fibers such as polyester and/or nylon compared tocotton. Suitable dyes include small molecule dyes and polymeric dyes.Suitable small molecule dyes include small molecule dyes selected fromthe group consisting of dyes falling into the Colour Index (C.I.)classifications of Direct Blue, Direct Red, Direct Violet, Acid Blue,Acid Red, Acid Violet, Basic Blue, Basic Violet and Basic Red, ormixtures thereof. Examples of small molecule dyes include those selectedfrom the group consisting of Colour Index (Society of Dyers andColourists, Bradford, UK) numbers Direct Violet 9, Direct Violet 35,Direct Violet 48, Direct Violet 51, Direct Violet 66, Direct Violet 99,Direct Blue 1, Direct Blue 71, Direct Blue 80, Direct Blue 279, Acid Red17, Acid Red 73, Acid Red 88, Acid Red 150, Acid Violet 15, Acid Violet17, Acid Violet 24, Acid Violet 43, Acid Red 52, Acid Violet 49, AcidViolet 50, Acid Blue 15, Acid Blue 17, Acid Blue 25, Acid Blue 29, AcidBlue 40, Acid Blue 45, Acid Blue 75, Acid Blue 80, Acid Blue 83, AcidBlue 90 and Acid Blue 113, Acid Black 1, Basic Violet 1, Basic Violet 3,Basic Violet 4, Basic Violet 10, Basic Violet 35, Basic Blue 3, BasicBlue 16, Basic Blue 22, Basic Blue 47, Basic Blue 66, Basic Blue 75,Basic Blue 159, small molecule dyes selected from the group consistingof Colour Index (Society of Dyers and Colourists, Bradford, UK) numbersAcid Violet 17, Acid Violet 43, Acid Red 52, Acid Red 73, Acid Red 88,Acid Red 150, Acid Blue 25, Acid Blue 29, Acid Blue 45, Acid Blue 113,Acid Black 1, Direct Blue 1, Direct Blue 71. Direct Violet smallmolecule dyes may be preferred. Dyes selected from the group consistingAcid Violet 17, Direct Blue 71, Direct Violet 51, Direct Blue 1, AcidRed 88, Acid Red 150, Acid Blue 29, Acid Blue 113 and mixtures thereofmay be preferred.

Suitable polymeric dyes include polymeric dyes selected from the groupconsisting of polymers containing covalently bound chromogens(dye-polymer conjugates) and polymers with chromogens co-polymerizedinto the backbone of the polymer and mixtures thereof, and polymericdyes selected from the group consisting of fabric-substantive colorantssold under the name of Liquitint® (Milliken & Company, Spartanburg,S.C., USA), dye-polymer conjugates formed from at least one reactive dyeand a polymer selected from the group consisting of polymers comprisinga moiety selected from the group consisting of a hydroxyl moiety, aprimary amine moiety, a secondary amine moiety, a thiol moiety andmixtures thereof. In still another aspect, suitable polymeric dyesinclude polymeric dyes selected from the group consisting of Liquitint®(Milliken & Company, Spartanburg, S.C., USA) Violet CT, carboxymethylcellulose (CMC) conjugated with a reactive blue, reactive violet orreactive red dye such as CMC conjugated with C.I. Reactive Blue 19, soldby Megazyme, Wicklow, Ireland under the product name AZO-CM-CELLULOSE,product code S-ACMC, alkoxylated triphenyl-methane polymeric colorants,alkoxylated thiophene polymeric colorants, and mixtures thereof.Preferred additional hueing dyes include the whitening agents found inWO 08/87497 A1. These whitening agents may be characterized by thefollowing structure (IV):

wherein R₁ and R₂ can independently be selected from:

a) [(CH₂CR′HO)_(x)(CH₂CR″HO)_(y)H], wherein R′ is selected from thegroup consisting of H, CH₃, CH₂O(CH₂CH₂O)_(z)H, and mixtures thereof;wherein R″ is selected from the group consisting of H,CH₂O(CH₂CH₂O)_(z)H, and mixtures thereof; wherein x+y≤5; wherein y≥1;and wherein z=0 to 5;

b) R₁=alkyl, aryl or aryl alkyl and R₂=[(CH₂CR′HO)_(x)(CH₂CR″HO)_(y)H]wherein R′ is selected from the group consisting of H, CH₃,CH₂O(CH₂CH₂O)_(z)H, and mixtures thereof; wherein R″ is selected fromthe group consisting of H, CH₂O(CH₂CH₂O)_(z)H, and mixtures thereof;wherein x+y≤10; wherein y≥1; and wherein z=0 to 5;

c) R₁=[CH₂CH(OR₃)CH₂OR₄] and R₂=[CH₂CH(OR₃)CH₂O R₄]

wherein R₃ is selected from the group consisting of H, (CH₂CH₂O)_(z)H,and mixtures thereof; and wherein z=0 to 10;

wherein R₄ is selected from the group consisting of (C₁-C₁₆)alkyl, arylgroups, and mixtures thereof; and

d) wherein R₁ and R₂ can independently be selected from the aminoaddition product of styrene oxide, glycidyl methyl ether, isobutylglycidyl ether, isopropylglycidyl ether, t-butyl glycidyl ether,2-ethylhexylgycidyl ether, and glycidylhexadecyl ether, followed by theaddition of from 1 to 10 alkylene oxide units.

A preferred additional fabric hueing agent which may be incorporatedinto the compositions of the invention may be characterized by thefollowing structure (IV):

wherein R′ is selected from the group consisting of H, CH₃,CH₂O(CH₂CH₂O)_(z)H, and mixtures thereof; wherein R″ is selected fromthe group consisting of H, CH₂O(CH₂CH₂O)_(z)H, and mixtures thereof;wherein x+y≤5; wherein y≥1; and wherein z=0 to 5.

A further preferred additional hueing dye may be characterized by thefollowing structure (V):

This dye is typically a mixture of compounds having an average of 3-10EO groups, preferably 5 EO groups per molecule.

Further additional shading dyes are those described in USPN 2008 34511A1 (Unilever). A preferred agent is “Solvent Violet 13”.

In one aspect, additional hueing dyes include, without limitation,Liquitint® (Milliken & Company, Spartanburg, S.C., USA) Violet CT,Violet 200, Violet ION, E4210, Blue 452, Direct Violet 9, Direct Violet66, Solvent Violet 13, Acid Violet 50, and mixtures thereof. Suitableadditional hueing dyes are further described in one or more of thefollowing: U.S. Pat. Nos. 7,642,282; 8,022,100; 8,138,222; 8,378,083;8,536,218; 8,962,815; 9,028,561; 9,068,081; 9,163,146; and US Pat. Pub.Nos. 2013/0303428A1, 2014/0371435A1, and 2015/0232789A1.

Suitable dye clay conjugates include dye clay conjugates selected fromthe group comprising at least one cationic/basic dye and a smectiteclay, and mixtures thereof. In another aspect, suitable dye clayconjugates include dye clay conjugates selected from the groupconsisting of one cationic/basic dye selected from the group consistingof C.I. Basic Yellow 1 through 108, C.I. Basic Orange 1 through 69, C.I.Basic Red 1 through 118, C.I. Basic Violet 1 through 51, C.I. Basic Blue1 through 164, C.I. Basic Green 1 through 14, C.I. Basic Brown 1 through23, CI Basic Black 1 through 11, and a clay selected from the groupconsisting of Montmorillonite clay, Hectorite clay, Saponite clay andmixtures thereof. In still another aspect, suitable dye clay conjugatesinclude dye clay conjugates selected from the group consisting of:Montmorillonite Basic Blue B7 C.I. 42595 conjugate, MontmorilloniteBasic Blue B9 C.I. 52015 conjugate, Montmorillonite Basic Violet V3 C.I.42555 conjugate, Montmorillonite Basic Green G1 C.I. 42040 conjugate,Montmorillonite Basic Red R1 C.I. 45160 conjugate, Montmorillonite C.I.Basic Black 2 conjugate, Hectorite Basic Blue B7 C.I. 42595 conjugate,Hectorite Basic Blue B9 C.I. 52015 conjugate, Hectorite Basic Violet V3C.I. 42555 conjugate, Hectorite Basic Green G1 C.I. 42040 conjugate,Hectorite Basic Red R1 C.I. 45160 conjugate, Hectorite C.I. Basic Black2 conjugate, Saponite Basic Blue B7 C.I. 42595 conjugate, Saponite BasicBlue B9 C.I. 52015 conjugate, Saponite Basic Violet V3 C.I. 42555conjugate, Saponite Basic Green G1 C.I. 42040 conjugate, Saponite BasicRed R1 C.I. 45160 conjugate, Saponite C.I. Basic Black 2 conjugate andmixtures thereof.

Suitable pigments include pigments selected from the group consisting offlavanthrone, indanthrone, chlorinated indanthrone containing from 1 to4 chlorine atoms, pyranthrone, dichloropyranthrone,monobromodichloropyranthrone, dibromodichloropyranthrone,tetrabromopyranthrone, perylene-3,4,9,10-tetracarboxylic acid diimide,wherein the imide groups may be unsubstituted or substituted byC₁-C₃-alkyl or a phenyl or heterocyclic radical, and wherein the phenyland heterocyclic radicals may additionally carry substituents which donot confer solubility in water, anthrapyrimidinecarboxylic acid amides,violanthrone, isoviolanthrone, dioxazine pigments, copper phthalocyaninewhich may contain up to 2 chlorine atoms per molecule, polychloro-copperphthalocyanine or polybromochloro-copper phthalocyanine containing up to14 bromine atoms per molecule and mixtures thereof. Particularlypreferred are Pigment Blues 15 to 20, especially Pigment Blue 15 and/or16. Other suitable pigments include those selected from the groupconsisting of Ultramarine Blue (CI Pigment Blue 29), Ultramarine Violet(CI. Pigment Violet 15) and mixtures thereof. Suitable hueing agents aredescribed in more detail in U.S. Pat. No. 7,208,459 B2, WO2012/054835,WO2009/069077, WO2012/166768.

Aesthetic Colorants.

The composition may comprise one or more aesthetic colorants. Suitableaesthetic colorants include dyes, dye-clay conjugates, pigments, andLiquitint® polymeric colorants (Milliken & Company, Spartanburg, S.C.,USA). In one aspect, suitable dyes and pigments include small moleculedyes and polymeric dyes. In another aspect, the aesthetic colorants arealkoxylated versions of any of the dye molecules disclosed herein. Theaesthetic colorant may include at least one chromophore constituentselected from the group consisting of acridines, anthraquinones, azines,azos, benzodifuranes, benzodifuranones, carotenoids, coumarins,cyanines, diazahemicyanines, diphenylmethanes, formazans, hemicyanines,indigoids, methanes, methines, naphthalimides, naphthoquinones, nitros,nitrosos, oxazines, phenothiazine, phthalocyanines (such as copperphthalocyanines), pyrazoles, pyrazolones, quinolones, stilbenes,styryls, triarylmethanes (such as triphenylmethanes), xanthenes, andmixtures thereof. Examples of these dyes or pigments may be selectedfrom the group consisting of Colour Index (Society of Dyers andColourists, Bradford, UK) numbers listed in the following table:

CI name Exemplary Commercial name CI number pigment blue 29 VibracolorBlue PBL 19 CI77007 Acid blue 182 Iragon Blue ABL 182 Acid blue 225Iragon Blue ABL 225 AB80 Iragon Blue ABL 80 PB15 Vibracolor Blue PBL 80pigment blue 15 Vibracolor Blue PBL15, Vibracolor CI 74160 PBL15-Lpigment blue 15:1 CI 74160 Pigment 15:3 Blue PBL 15:3 CI 74160 Acid Blue9 Iragon Blue ABL 9 CI 42090 Food Blue 5 Vibracolor Blue FBL5 CI 42051Direct Blue 86 Iragon Blue DBL 86 CI 74180 Pigment Green 7 Iragon GreenPGR7 CI 74260 Acid Green 25 Vibracolor AGR25 CI 61570 Food Green 3Puricolor Green U3 CI 42053 Solvent Green Puricolor Green SGR7 CI 59040Pigment Yellow 3 Iragon Yellow PYE3-L CI 11710 Food Yellow 13 VibracolorYellow FYE13 CI 47005 Pigment Yellow 1 Iragon Yellow PYE1-L CI 11680Acid Yellow 17 Vibracolor Yellow AYE17 CI 18965 Direct Yellow 13Vibracolor PYE 13-L CI 21100 Direct Yellow 28 Iragon Yellow DYE28 CI19555 Acid yellow 23 Iragon Yellow AYE23 CI 19140 Pigment Yellow 42Iragon Yellow 42-L CI 77492 Food Yellow 3 Puricolor Yellow FYE3 CI 13015Acid Yellow 36 Iragon Yellow AYE36 HFC CI 13065 Acid Red 14 PuricolorRed ARE14 CI 14720 Acid Orange 7 Puricolor Orange AOR7 FDA CI 15510Sanolin Lave Yellow 6X Sanolin Lave Yellow 6A Sanolin Lave Orange RSanolin Lave Red B Sanolin Lave Pink B Sanolin Lave Violet B SanolinLave Blue A Sanolin Lave Blue T Sanolin Lave Blue R Sanolin Lave Green GAcid Yellow 3 Sanolin Yellow C-362 CI 47005 Acid Yellow 17 SanolinYellow E-26L CI 18965 Acid Yellow 184 Sanolin Brilliant Flavine, SanolinBrilliant 86Z Direct Yellow 28 Sanolin Yellow B6 Acid Red 52 SanolinRhodamine B090, Sanolin CI 45100 Rhodamine C-B Acid Red 249 SanolinBrilliant Red NB6 Acid Violet 48 Sanolin Violet FBL S6R Acid Violet 126Sanolin Violet E2R S6R Acid Blue 9 Sanolin Blue V56, Sanolin Blue V56 CI42090 liquid Acid Blue 80 Sanolin Blue C-NBL S6R CI 61585 Acid Blue 182Sanolin Blue E-HRL Direct Blue 86 Sanolin Fast Turquoise 6LC CI 74180Direct Blue 199 Sanolin Turquois FBL Acid Green 25 Sanolin Green C-6L CI61570 Acid Green 28 Sanolin Brilliant Green R612, Sanolin BrilliantGreen R-36

In one aspect of the invention, aesthetic colorants include Liquitint®Blue AH, Liquitint® Blue BB, Liquitint® Blue 275, Liquitint® Blue 297,Liquitint® Blue BB, Cyan 15, Liquitint® Green 101, Liquitint® Orange272, Liquitint® Orange 255, Liquitint® Pink AM, Liquitint® Pink AMC,Liquitint® Pink ST, Liquitint® Violet 129, Liquitint® Violet LS,Liquitint® Violet 291, Liquitint® Yellow FT, Liquitint® Blue Buf,Liquitint® Pink AM, Liquitint® Pink PV, Acid Blue 80, Acid Blue 182,Acid Red 33, Acid Red 52, Acid Violet 48, Acid Violet 126, Acid Blue 9,Acid Blue 1, and mixtures thereof.

Encapsulates.

The composition may comprise an encapsulated material. In one aspect, anencapsulate comprising a core, a shell having an inner and outersurface, said shell encapsulating said core. The core may comprise anylaundry care adjunct, though typically the core may comprise materialselected from the group consisting of perfumes; brighteners; dyes;insect repellants; silicones; waxes; flavors; vitamins; fabric softeningagents; skin care agents in one aspect, paraffins; enzymes;anti-bacterial agents; bleaches; sensates; and mixtures thereof; andsaid shell may comprise a material selected from the group consisting ofpolyethylenes; polyamides; polyvinylalcohols, optionally containingother co-monomers; polystyrenes; polyisoprenes; polycarbonates;polyesters; polyacrylates; aminoplasts, in one aspect said aminoplastmay comprise a polyureas, polyurethane, and/or polyureaurethane, in oneaspect said polyurea may comprise polyoxymethyleneurea and/or melamineformaldehyde; polyolefins; polysaccharides, in one aspect saidpolysaccharide may comprise alginate and/or chitosan; gelatin; shellac;epoxy resins; vinyl polymers; water insoluble inorganics; silicone; andmixtures thereof. Preferred encapsulates comprise perfume. Preferredencapsulates comprise a shell which may comprise melamine formaldehydeand/or cross linked melamine formaldehyde. Preferred encapsulatescomprise a core material and a shell, said shell at least partiallysurrounding said core material, is disclosed. At least 75%, 85% or even90% of said encapsulates may have a fracture strength of from 0.2 MPa to10 MPa, and a benefit agent leakage of from 0% to 20%, or even less than10% or 5% based on total initial encapsulated benefit agent. Preferredare those in which at least 75%, 85% or even 90% of said encapsulatesmay have (i) a particle size of from 1 microns to 80 microns, 5 micronsto 60 microns, from 10 microns to 50 microns, or even from 15 microns to40 microns, and/or (ii) at least 75%, 85% or even 90% of saidencapsulates may have a particle wall thickness of from 30 nm to 250 nm,from 80 nm to 180 nm, or even from 100 nm to 160 nm. Formaldehydescavengers may be employed with the encapsulates, for example, in acapsule slurry and/or added to a composition before, during or after theencapsulates are added to such composition. Suitable capsules that canbe made by following the teaching of USPA 2008/0305982 A1; and/or USPA2009/0247449 A1. Alternatively, suitable capsules can be purchased fromAppleton Papers Inc. of Appleton, Wis. USA.

In a preferred aspect the composition may comprise a deposition aid,preferably in addition to encapsulates. Preferred deposition aids areselected from the group consisting of cationic and nonionic polymers.Suitable polymers include cationic starches, cationichydroxyethylcellulose, polyvinylformaldehyde, locust bean gum, mannans,xyloglucans, tamarind gum, polyethyleneterephthalate and polymerscontaining dimethylaminoethyl methacrylate, optionally with one or moremonomers selected from the group comprising acrylic acid and acrylamide.

Perfume.

Preferred compositions of the invention comprise perfume. Typically thecomposition comprises a perfume that comprises one or more perfume rawmaterials, selected from the group as described in WO08/87497. However,any perfume useful in a laundry care composition may be used. Apreferred method of incorporating perfume into the compositions of theinvention is via an encapsulated perfume particle comprising either awater-soluble hydroxylic compound or melamine-formaldehyde or modifiedpolyvinyl alcohol. In one aspect the encapsulate comprises (a) an atleast partially water-soluble solid matrix comprising one or morewater-soluble hydroxylic compounds, preferably starch; and (b) a perfumeoil encapsulated by the solid matrix. In a further aspect the perfumemay be pre-complexed with a polyamine, preferably a polyethylenimine soas to form a Schiff base.

Polymers.

The composition may comprise one or more polymers. Examples areoptionally modified carboxymethylcellulose, poly(vinyl-pyrrolidone),poly (ethylene glycol), poly(vinyl alcohol),poly(vinylpyridine-N-oxide), poly(vinylimidazole), polycarboxylates suchas polyacrylates, maleic/acrylic acid copolymers and laurylmethacrylate/acrylic acid co-polymers.

The composition may comprise one or more amphiphilic cleaning polymerssuch as the compound having the following general structure:bis((C₂H₅O)(C₂H₄O)n)(CH₃)—N+—C_(x)H_(2x)—N⁺—(CH₃)-bis((C₂H₅O)(C₂H₄O)n),wherein n=from 20 to 30, and x=from 3 to 8, or sulphated or sulphonatedvariants thereof. In one aspect, this polymer is sulphated orsulphonated to provide a zwitterionic soil suspension polymer.

The composition preferably comprises amphiphilic alkoxylated greasecleaning polymers which have balanced hydrophilic and hydrophobicproperties such that they remove grease particles from fabrics andsurfaces. Preferred amphiphilic alkoxylated grease cleaning polymerscomprise a core structure and a plurality of alkoxylate groups attachedto that core structure. These may comprise alkoxylatedpolyalkyleneimines, preferably having an inner polyethylene oxide blockand an outer polypropylene oxide block. Typically these may beincorporated into the compositions of the invention in amounts of from0.005 to 10 wt %, generally from 0.5 to 8 wt %.

Alkoxylated polycarboxylates such as those prepared from polyacrylatesare useful herein to provide additional grease removal performance. Suchmaterials are described in WO 91/08281 and PCT 90/01815. Chemically,these materials comprise polyacrylates having one ethoxy side-chain perevery 7-8 acrylate units. The side-chains are of the formula—(CH₂CH₂O)_(m), (CH₂)_(n)CH₃ wherein m is 2-3 and n is 6-12. Theside-chains are ester-linked to the polyacrylate “backbone” to provide a“comb” polymer type structure. The molecular weight can vary, but istypically in the range of about 2000 to about 50,000. Such alkoxylatedpolycarboxylates can comprise from about 0.05% to about 10%, by weight,of the compositions herein.

Mixtures of cosurfactants and other adjunct ingredients, areparticularly suited to be used with an amphiphilic graft co-polymer.Preferred amphiphilic graft co-polymer(s) comprise (i) polyethyleneglycol backbone; and (ii) and at least one pendant moiety selected frompolyvinyl acetate, polyvinyl alcohol and mixtures thereof. A preferredamphiphilic graft co-polymer is Sokalan HP22, supplied from BASF.Suitable polymers include random graft copolymers, preferably apolyvinyl acetate grafted polyethylene oxide copolymer having apolyethylene oxide backbone and multiple polyvinyl acetate side chains.The molecular weight of the polyethylene oxide backbone is preferablyabout 6000 and the weight ratio of the polyethylene oxide to polyvinylacetate is about 40 to 60 and no more than 1 grafting point per 50ethylene oxide units. Typically these are incorporated into thecompositions of the invention in amounts from 0.005 to 10 wt %, moreusually from 0.05 to 8 wt %. Preferably the composition comprises one ormore carboxylate polymer, such as a maleate/acrylate random copolymer orpolyacrylate homopolymer. In one aspect, the carboxylate polymer is apolyacrylate homopolymer having a molecular weight of from 4,000 Da to9,000 Da, or from 6,000 Da to 9,000 Da. Typically these are incorporatedinto the compositions of the invention in amounts from 0.005 to 10 wt %,or from 0.05 to 8 wt %.

Preferably the composition comprises one or more soil release polymers.Examples include soil release polymers having a structure as defined byone of the following Formula (VI), (VII) or (VIII):—[(OCHR¹—CHR²)_(a)—O—OC—Ar—CO—]_(d)  (VI)—[(OCHR³—CHR⁴)_(b)—O—OC-sAr—CO—]_(e)  (VII)—[(OCHR⁵—CHR⁶)_(c)—OR⁷]_(f)  (VIII)

wherein:

a, b and c are from 1 to 200;

d, e and f are from 1 to 50;

Ar is a 1,4-substituted phenylene;

sAr is 1,3-substituted phenylene substituted in position 5 with SO₃Me;

Me is Li, K, Mg/2, Ca/2, Al/3, ammonium, mono-, di-, tri-, ortetraalkylammonium wherein the alkyl groups are C₁-C₁₈ alkyl or C₂-C₁₀hydroxyalkyl, or mixtures thereof;

R¹, R², R³, R⁴, R⁵ and R⁶ are independently selected from H or C₁-C₁₈ n-or iso-alkyl; and

R⁷ is a linear or branched C₁-C₁₈ alkyl, or a linear or branched C₂-C₃₀alkenyl, or a cycloalkyl group with 5 to 9 carbon atoms, or a C₈-C₃₀aryl group, or a C₆-C₃₀ arylalkyl group.

Suitable soil release polymers are polyester soil release polymers suchas Repel-o-tex polymers, including Repel-o-tex SF, SF-2 and SRP6supplied by Rhodia. Other suitable soil release polymers include Texcarepolymers, including Texcare SRA100, SRA300, SRN100, SRN170, SRN240,SRN300 and SRN325 supplied by Clariant. Other suitable soil releasepolymers are Marloquest polymers, such as Marloquest SL supplied bySasol.

Preferably the composition comprises one or more cellulosic polymer,including those selected from alkyl cellulose, alkyl alkoxyalkylcellulose, carboxyalkyl cellulose, alkyl carboxyalkyl cellulose.Preferred cellulosic polymers are selected from the group comprisingcarboxymethyl cellulose, methyl cellulose, methyl hydroxyethylcellulose, methyl carboxymethyl cellulose, and mixtures thereof. In oneaspect, the carboxymethyl cellulose has a degree of carboxymethylsubstitution from 0.5 to 0.9 and a molecular weight from 100,000 Da to300,000 Da.

Enzymes.

Preferably the composition comprises one or more enzymes. Preferredenzymes provide cleaning performance and/or fabric care benefits.Examples of suitable enzymes include, but are not limited to,hemicellulases, peroxidases, proteases, cellulases, xylanases, lipases,phospholipases, esterases, cutinases, pectinases, mannanases, pectatelyases, keratinases, reductases, oxidases, phenoloxidases,lipoxygenases, ligninases, pullulanases, tannases, pentosanases,malanases, ß-glucanases, arabinosidases, hyaluronidase, chondroitinase,laccase, and amylases, or mixtures thereof. A typical combination is anenzyme cocktail that may comprise, for example, a protease and lipase inconjunction with amylase. When present in the composition, theaforementioned additional enzymes may be present at levels from about0.00001% to about 2%, from about 0.0001% to about 1% or even from about0.001% to about 0.5% enzyme protein by weight of the composition.

Proteases.

Preferably the composition comprises one or more proteases. Suitableproteases include metalloproteases and serine proteases, includingneutral or alkaline microbial serine proteases, such as subtilisins (EC3.4.21.62). Suitable proteases include those of animal, vegetable ormicrobial origin. In one aspect, such suitable protease may be ofmicrobial origin. The suitable proteases include chemically orgenetically modified mutants of the aforementioned suitable proteases.In one aspect, the suitable protease may be a serine protease, such asan alkaline microbial protease or/and a trypsin-type protease. Examplesof suitable neutral or alkaline proteases include:

(a) subtilisins (EC 3.4.21.62), including those derived from Bacillus,such as Bacillus lentus, B. alkalophilus, B. subtilis, B.amyloliquefaciens, Bacillus pumilus and Bacillus gibsonii described inU.S. Pat. No. 6,312,936 B1, U.S. Pat. Nos. 5,679,630, 4,760,025,7,262,042 and WO09/021867.

(b) trypsin-type or chymotrypsin-type proteases, such as trypsin (e.g.,of porcine or bovine origin), including the Fusarium protease describedin WO 89/06270 and the chymotrypsin proteases derived from Cellumonasdescribed in WO 05/052161 and WO 05/052146.

(c) metalloproteases, including those derived from Bacillusamyloliquefaciens described in WO 07/044993A2.

Preferred proteases include those derived from Bacillus gibsonii orBacillus Lentus.

Suitable commercially available protease enzymes include those soldunder the trade names Alcalase®, Savinase®, Primase®, Durazym®,Polarzyme®, Kannase®, Liquanase®, Liquanase Ultra®, Savinase Ultra®,Ovozyme®, Neutrase®, Everlase® and Esperase® by Novozymes A/S (Denmark),those sold under the tradename Maxatase®, Maxacal®, Maxapem®,Properase®, Purafect®, Purafect Prime®, Purafect Ox®, FN3®, FN4®,Excellase® and Purafect OXP® by Genencor International, those sold underthe tradename Opticlean® and Optimase® by Solvay Enzymes, thoseavailable from Henkel/Kemira, namely BLAP (sequence shown in FIG. 29 ofU.S. Pat. No. 5,352,604 with the following mutations S99D+S101R+S103A+V1041+G159S, hereinafter referred to as BLAP), BLAP R (BLAP withS3T+V41+V199M+V2051+L217D), BLAP X (BLAP with S3T+V41+V2051) and BLAPF49 (BLAP with S3T+V41+A194P+V199M+V2051+L217D)—all from Henkel/Kemira;and KAP (Bacillus alkalophilus subtilisin with mutationsA230V+S256G+S259N) from Kao.

Amylases.

Preferably the composition may comprise an amylase. Suitablealpha-amylases include those of bacterial or fungal origin. Chemicallyor genetically modified mutants (variants) are included. A preferredalkaline alpha-amylase is derived from a strain of Bacillus, such asBacillus licheniformis, Bacillus amyloliquefaciens, Bacillusstearothermophilus, Bacillus subtilis, or other Bacillus sp., such asBacillus sp. NCIB 12289, NCIB 12512, NCIB 12513, DSM 9375 (U.S. Pat. No.7,153,818) DSM 12368, DSMZ no. 12649, KSM AP1378 (WO 97/00324), KSM K36or KSM K38 (EP 1,022,334). Preferred amylases include:

(a) the variants described in WO 94/02597, WO 94/18314, WO96/23874 andWO 97/43424, especially the variants with substitutions in one or moreof the following positions versus the enzyme listed as SEQ ID No. 2 inWO 96/23874: 15, 23, 105, 106, 124, 128, 133, 154, 156, 181, 188, 190,197, 202, 208, 209, 243, 264, 304, 305, 391, 408, and 444.

(b) the variants described in U.S. Pat. No. 5,856,164 and WO99/23211, WO96/23873, WO00/60060 and WO 06/002643, especially the variants with oneor more substitutions in the following positions versus the AA560 enzymelisted as SEQ ID No. 12 in WO 06/002643:

26, 30, 33, 82, 37, 106, 118, 128, 133, 149, 150, 160, 178, 182, 186,193, 203, 214, 231, 256, 257, 258, 269, 270, 272, 283, 295, 296, 298,299, 303, 304, 305, 311, 314, 315, 318, 319, 339, 345, 361, 378, 383,419, 421, 437, 441, 444, 445, 446, 447, 450, 461, 471, 482, 484,preferably that also contain the deletions of D183* and G184*.

(c) variants exhibiting at least 90% identity with SEQ ID No. 4 inWO06/002643, the wild-type enzyme from Bacillus SP722, especiallyvariants with deletions in the 183 and 184 positions and variantsdescribed in WO 00/60060, which is incorporated herein by reference.

(d) variants exhibiting at least 95% identity with the wild-type enzymefrom Bacillus sp. 707 (SEQ ID NO:7 in U.S. Pat. No. 6,093,562),especially those comprising one or more of the following mutations M202,M208, S255, R172, and/or M261. Preferably said amylase comprises one ormore of M202L, M202V, M2025, M2021, M2021, M202Q, M202W, S255N and/orR172Q. Particularly preferred are those comprising the M202L or M2021mutations.

(e) variants described in WO 09/149130, preferably those exhibiting atleast 90% identity with SEQ ID NO: 1 or SEQ ID NO:2 in WO 09/149130, thewild-type enzyme from Geobacillus stearophermophilus or a truncatedversion thereof.

Suitable commercially available alpha-amylases include DURAMYL®,LIQUEZYME®, TERMAMYL®, TERMAMYL ULTRA®, NATALASE®, SUPRAMYL®,STAINZYME®, STAINZYME PLUS®, FUNGAMYL® and BAN® (Novozymes A/S,Bagsvaerd, Denmark), KEMZYM® AT 9000 Biozym Biotech Trading GmbHWehlistrasse 27b A-1200 Wien Austria, RAPIDASE®, PURASTAR®, ENZYSIZE®,OPTISIZE HT PLUS®, POWERASE® and PURASTAR OXAM® (Genencor InternationalInc., Palo Alto, Calif.) and KAM® (Kao, 14-10 Nihonbashi Kayabacho,1-chome, Chuo-ku Tokyo 103-8210, Japan). In one aspect, suitableamylases include NATALASE®, STAINZYME® and STAINZYME PLUS® and mixturesthereof.

Lipases.

Preferably the invention comprises one or more lipases, including “firstcycle lipases” such as those described in U.S. Pat. No. 6,939,702 B1 andUS PA 2009/0217464. Preferred lipases are first-wash lipases. In oneembodiment of the invention the composition comprises a first washlipase. First wash lipases includes a lipase which is a polypeptidehaving an amino acid sequence which: (a) has at least 90% identity withthe wild-type lipase derived from Humicola lanuginosa strain DSM 4109;(b) compared to said wild-type lipase, comprises a substitution of anelectrically neutral or negatively charged amino acid at the surface ofthe three-dimensional structure within 15A of E1 or Q249 with apositively charged amino acid; and (c) comprises a peptide addition atthe C-terminal; and/or (d) comprises a peptide addition at theN-terminal and/or (e) meets the following limitations: i) comprises anegative amino acid in position E210 of said wild-type lipase; ii)comprises a negatively charged amino acid in the region corresponding topositions 90-101 of said wild-type lipase; and iii) comprises a neutralor negative amino acid at a position corresponding to N94 or saidwild-type lipase and/or has a negative or neutral net electric charge inthe region corresponding to positions 90-101 of said wild-type lipase.Preferred are variants of the wild-type lipase from Thermomyceslanuginosus comprising one or more of the T231R and N233R mutations. Thewild-type sequence is the 269 amino acids (amino acids 23-291) of theSwissprot accession number Swiss-Prot 059952 (derived from Thermomyceslanuginosus (Humicola lanuginosa)). Preferred lipases would includethose sold under the tradenames Lipex® and Lipolex® and Lipoclean®.

Endoglucanases.

Other preferred enzymes include microbial-derived endoglucanasesexhibiting endo-beta-1,4-glucanase activity (E.C. 3.2.1.4), including abacterial polypeptide endogenous to a member of the genus Bacillus whichhas a sequence of at least 90%, 94%, 97% and even 99% identity to theamino acid sequence SEQ ID NO:2 in U.S. Pat. No. 7,141,403B2) andmixtures thereof. Suitable endoglucanases are sold under the tradenamesCelluclean® and Whitezyme® (Novozymes A/S, Bagsvaerd, Denmark).

Pectate Lyases.

Other preferred enzymes include pectate lyases sold under the tradenamesPectawash®, Pectaway®, Xpect® and mannanases sold under the tradenamesMannaway® (all from Novozymes A/S, Bagsvaerd, Denmark), and Purabrite®(Genencor International Inc., Palo Alto, Calif.).

Bleaching Agents.

It may be preferred for the composition to comprise one or morebleaching agents. Suitable bleaching agents other than bleachingcatalysts include photobleaches, bleach activators, hydrogen peroxide,sources of hydrogen peroxide, pre-formed peracids and mixtures thereof.In general, when a bleaching agent is used, the compositions of thepresent invention may comprise from about 0.1% to about 50% or even fromabout 0.1% to about 25% bleaching agent or mixtures of bleaching agentsby weight of the subject composition. Examples of suitable bleachingagents include:

(1) photobleaches for example sulfonated zinc phthalocyanine sulfonatedaluminium phthalocyanines, xanthene dyes and mixtures thereof;

(2) pre-formed peracids: Suitable preformed peracids include, but arenot limited to compounds selected from the group consisting ofpre-formed peroxyacids or salts thereof typically a percarboxylic acidsand salts, percarbonic acids and salts, perimidic acids and salts,peroxymonosulfuric acids and salts, for example, Oxone®, and mixturesthereof. Suitable examples include peroxycarboxylic acids or saltsthereof, or peroxysulphonic acids or salts thereof. Typicalperoxycarboxylic acid salts suitable for use herein have a chemicalstructure corresponding to the following chemical formula:

wherein: R¹⁴ is selected from alkyl, aralkyl, cycloalkyl, aryl orheterocyclic groups; the R¹⁴ group can be linear or branched,substituted or unsubstituted; having, when the peracid is hydrophobic,from 6 to 14 carbon atoms, or from 8 to 12 carbon atoms and, when theperacid is hydrophilic, less than 6 carbon atoms or even less than 4carbon atoms and Y is any suitable counter-ion that achieves electriccharge neutrality, preferably Y is selected from hydrogen, sodium orpotassium. Preferably, R¹⁴ is a linear or branched, substituted orunsubstituted C₆₋₉ alkyl. Preferably, the peroxyacid or salt thereof isselected from peroxyhexanoic acid, peroxyheptanoic acid, peroxyoctanoicacid, peroxynonanoic acid, peroxydecanoic acid, any salt thereof, or anycombination thereof. Particularly preferred peroxyacids arephthalimido-peroxy-alkanoic acids, in particular ε-phthalimido peroxyhexanoic acid (PAP). Preferably, the peroxyacid or salt thereof has amelting point in the range of from 30° C. to 60° C.

The pre-formed peroxyacid or salt thereof can also be a peroxysulphonicacid or salt thereof, typically having a chemical structurecorresponding to the following chemical formula:

wherein: R¹⁵ is selected from alkyl, aralkyl, cycloalkyl, aryl orheterocyclic groups; the R¹⁵ group can be linear or branched,substituted or unsubstituted; and Z is any suitable counter-ion thatachieves electric charge neutrality, preferably Z is selected fromhydrogen, sodium or potassium. Preferably R¹⁵ is a linear or branched,substituted or unsubstituted C₄₋₁₄, preferably C₆₋₁₄ alkyl. Preferablysuch bleach components may be present in the compositions of theinvention in an amount from 0.01 to 50%, most preferably from 0.1% to20%.

(3) sources of hydrogen peroxide, for example, inorganic perhydratesalts, including alkali metal salts such as sodium salts of perborate(usually mono- or tetra-hydrate), percarbonate, persulphate,perphosphate, persilicate salts and mixtures thereof. In one aspect ofthe invention the inorganic perhydrate salts are selected from the groupconsisting of sodium salts of perborate, percarbonate and mixturesthereof. When employed, inorganic perhydrate salts are typically presentin amounts of from 0.05 to 40 wt %, or 1 to 30 wt % of the overallfabric and home care product and are typically incorporated into suchfabric and home care products as a crystalline solid that may be coated.Suitable coatings include, inorganic salts such as alkali metalsilicate, carbonate or borate salts or mixtures thereof, or organicmaterials such as water-soluble or dispersible polymers, waxes, oils orfatty soaps; and

(4) bleach activators having R—(C═O)-L wherein R is an alkyl group,optionally branched, having, when the bleach activator is hydrophobic,from 6 to 14 carbon atoms, or from 8 to 12 carbon atoms and, when thebleach activator is hydrophilic, less than 6 carbon atoms or even lessthan 4 carbon atoms; and L is leaving group. Examples of suitableleaving groups are benzoic acid and derivatives thereof—especiallybenzene sulphonate. Suitable bleach activators include dodecanoyloxybenzene sulphonate, decanoyl oxybenzene sulphonate, decanoyloxybenzoic acid or salts thereof, 3,5,5-trimethyl hexanoyloxybenzenesulphonate, tetraacetyl ethylene diamine (TAED) and nonanoyloxybenzenesulphonate (NOBS). Suitable bleach activators are also disclosed in WO98/17767. While any suitable bleach activator may be employed, in oneaspect of the invention the subject composition may comprise NOBS, TAEDor mixtures thereof.

(5) Bleach Catalysts.

The compositions of the present invention may also include one or morebleach catalysts capable of accepting an oxygen atom from a peroxyacidand/or salt thereof, and transferring the oxygen atom to an oxidizeablesubstrate. Suitable bleach catalysts include, but are not limited to:iminium cations and polyions; iminium zwitterions; modified amines;modified amine oxides; N-sulphonyl imines; N-phosphonyl imines; N-acylimines; thiadiazole dioxides; perfluoroamines; cyclic sugar ketones andalpha amino-ketones and mixtures thereof. Suitable alpha amino ketonesare for example as described in WO 2012/000846 A1, WO 2008/015443 A1,and WO 2008/014965 A1. Suitable mixtures are as described in USPA2007/0173430 A1.

Without wishing to be bound by theory, the inventors believe thatcontrolling the electrophilicity and hydrophobicity in this abovedescribed manner enables the bleach ingredient to be deliveredsubstantially only to areas of the fabric that are more hydrophobic, andthat contain electron rich soils, including visible chromophores, thatare susceptible to bleaching by highly electrophilic oxidants.

In one aspect, the bleach catalyst has a structure corresponding togeneral formula below:

wherein R¹³ is selected from the group consisting of 2-ethylhexyl,2-propylheptyl, 2-butyloctyl, 2-pentylnonyl, 2-hexyldecyl, n-dodecyl,n-tetradecyl, n-hexadecyl, n-octadecyl, iso-nonyl, iso-decyl,iso-tridecyl and iso-pentadecyl;

(6) The composition may preferably comprise catalytic metal complexes.One preferred type of metal-containing bleach catalyst is a catalystsystem comprising a transition metal cation of defined bleach catalyticactivity, such as copper, iron, titanium, ruthenium, tungsten,molybdenum, or manganese cations, an auxiliary metal cation havinglittle or no bleach catalytic activity, such as zinc or aluminumcations, and a sequestrate having defined stability constants for thecatalytic and auxiliary metal cations, particularly ethylenediaminetetraacetic acid, ethylenediaminetetra(methylenephosphonic acid) andwater-soluble salts thereof. Such catalysts are disclosed in U.S. Pat.No. 4,430,243.

If desired, the compositions herein can be catalyzed by means of amanganese compound. Such compounds and levels of use are well known inthe art and include, for example, the manganese-based catalystsdisclosed in U.S. Pat. No. 5,576,282. Cobalt bleach catalysts usefulherein are known, and are described, for example, in U.S. Pat. Nos.5,597,936; 5,595,967. Such cobalt catalysts are readily prepared byknown procedures, such as taught for example in U.S. Pat. Nos.5,597,936, 5,595,967.

Compositions herein may also suitably include a transition metal complexof ligands such as bispidones (WO 05/042532 A1) and/or macropolycyclicrigid ligands—abbreviated as “MRLs”. As a practical matter, and not byway of limitation, the compositions and processes herein can be adjustedto provide on the order of at least one part per hundred million of theactive MRL species in the aqueous washing medium, and will typicallyprovide from about 0.005 ppm to about 25 ppm, from about 0.05 ppm toabout 10 ppm, or even from about 0.1 ppm to about 5 ppm, of the MRL inthe wash liquor.

Suitable transition-metals in the instant transition-metal bleachcatalyst include, for example, manganese, iron and chromium. SuitableMRLs include 5,12-diethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecane.

Suitable transition metal MRLs are readily prepared by known procedures,such as taught for example in WO 00/32601, and U.S. Pat. No. 6,225,464.

When present, the source of hydrogen peroxide/peracid and/or bleachactivator is generally present in the composition in an amount of fromabout 0.1 to about 60 wt %, from about 0.5 to about 40 wt % or even fromabout 0.6 to about 10 wt % based on the fabric and home care product.One or more hydrophobic peracids or precursors thereof may be used incombination with one or more hydrophilic peracid or precursor thereof.

Typically hydrogen peroxide source and bleach activator will beincorporated together. The amounts of hydrogen peroxide source andperacid or bleach activator may be selected such that the molar ratio ofavailable oxygen (from the peroxide source) to peracid is from 1:1 to35:1, or even 2:1 to 10:1.

Surfactant.

Preferably the composition comprises a surfactant or surfactant system.The surfactant can be selected from nonionic, anionic, cationic,amphoteric, ampholytic, amphiphilic, zwitterionic, semi-polar nonionicsurfactants and mixtures thereof. Preferred compositions comprise amixture of surfactants/surfactant system. Preferred surfactant systemscomprise one or more anionic surfactants, most preferably in combinationwith a co-surfactant, most preferably a nonionic and/or amphotericand/or zwitterionic surfactant. Preferred surfactant systems compriseboth anionic and nonionic surfactant, preferably in weight ratios from90:1 to 1:90. In some instances a weight ratio of anionic to nonionicsurfactant of at least 1:1 is preferred. However a ratio below 10:1 maybe preferred. When present, the total surfactant level is preferablyfrom 0.1% to 60%, from 1% to 50% or even from 5% to 40% by weight of thesubject composition.

Preferably the composition comprises an anionic detersive surfactant,preferably sulphate and/or sulphonate surfactants. Preferred examplesinclude alkyl benzene sulphonates, alkyl sulphates and alkyl alkoxylatedsulphates. Preferred sulphonates are C₁₀₋₁₃ alkyl benzene sulphonate.Suitable alkyl benzene sulphonate (LAS) may be obtained, by sulphonatingcommercially available linear alkyl benzene (LAB); suitable LAB includeslow 2-phenyl LAB, such as those supplied by Sasol under the tradenameIsochem® or those supplied by Petresa under the tradename Petrelab®,other suitable LAB include high 2-phenyl LAB, such as those supplied bySasol under the tradename Hyblene®. A suitable anionic detersivesurfactant is alkyl benzene sulphonate that is obtained by DETALcatalyzed process, although other synthesis routes, such as HF, may alsobe suitable. In one aspect a magnesium salt of LAS is used.

Preferred sulphate detersive surfactants include alkyl sulphate,typically C₈₋₁₈ alkyl sulphate, or predominantly C₁₂ alkyl sulphate. Afurther preferred alkyl sulphate is alkyl alkoxylated sulphate,preferably a C₈₋₁₈ alkyl alkoxylated sulphate. Preferably thealkoxylating group is an ethoxylating group. Typically the alkylalkoxylated sulphate has an average degree of alkoxylation of from 0.5to 30 or 20, or from 0.5 to 10. Particularly preferred are C₈₋₁₈ alkylethoxylated sulphate having an average degree of ethoxylation of from0.5 to 10, from 0.5 to 7, from 0.5 to 5 or even from 0.5 to 3.

The alkyl sulphate, alkyl alkoxylated sulphate and alkyl benzenesulphonates may be linear or branched, substituted or un-substituted.When the surfactant is branched, preferably the surfactant will comprisea mid-chain branched sulphate or sulphonate surfactant. Preferably thebranching groups comprise C₁₋₄ alkyl groups, typically methyl and/orethyl groups.

Preferably the composition comprises a nonionic detersive surfactant.Suitable non-ionic surfactants are selected from the group consistingof: C₈-C₁₈ alkyl ethoxylates, such as, NEODOL® non-ionic surfactantsfrom Shell; C₆-C₁₂ alkyl phenol alkoxylates wherein the alkoxylate unitsmay be ethyleneoxy units, propyleneoxy units or a mixture thereof;C₁₂-C₁₈ alcohol and C₆-C₁₂ alkyl phenol condensates with ethyleneoxide/propylene oxide block polymers such as Pluronic® from BASF;C₁₄-C₂₂ mid-chain branched alcohols; C₁₄-C₂₂ mid-chain branched alkylalkoxylates, typically having an average degree of alkoxylation of from1 to 30; alkylpolysaccharides, in one aspect, alkylpolyglycosides;polyhydroxy fatty acid amides; ether capped poly(oxyalkylated) alcoholsurfactants; and mixtures thereof.

Suitable non-ionic detersive surfactants include alkyl polyglucosideand/or an alkyl alkoxylated alcohol.

In one aspect, non-ionic detersive surfactants include alkyl alkoxylatedalcohols, in one aspect C₈₋₁₈ alkyl alkoxylated alcohol, for example aC₈₋₁₈ alkyl ethoxylated alcohol, the alkyl alkoxylated alcohol may havean average degree of alkoxylation of from 1 to 80, preferably from 1 to50, most preferably from 1 to 30, from 1 to 20, or from 1 to 10. In oneaspect, the alkyl alkoxylated alcohol may be a C₈₋₁₈ alkyl ethoxylatedalcohol having an average degree of ethoxylation of from 1 to 10, from 1to 7, more from 1 to 5 or from 3 to 7, or even below 3 or 2. The alkylalkoxylated alcohol can be linear or branched, and substituted orun-substituted.

Suitable nonionic surfactants include those with the trade nameLutensol® from BASF.

Suitable cationic detersive surfactants include alkyl pyridiniumcompounds, alkyl quaternary ammonium compounds, alkyl quaternaryphosphonium compounds, alkyl ternary sulphonium compounds, and mixturesthereof.

Suitable cationic detersive surfactants are quaternary ammoniumcompounds having the general formula:(R)(R₁)(R₂)(R₃)N⁺X⁻

wherein, R is a linear or branched, substituted or unsubstituted C₆₋₁₈alkyl or alkenyl moiety, R₁ and R₂ are independently selected frommethyl or ethyl moieties, R₃ is a hydroxyl, hydroxymethyl or ahydroxyethyl moiety, X is an anion which provides charge neutrality,suitable anions include: halides, for example chloride; sulphate; andsulphonate. Suitable cationic detersive surfactants are mono-C₆₋₁₈ alkylmono-hydroxyethyl di-methyl quaternary ammonium chlorides. Highlysuitable cationic detersive surfactants are mono-C₈₋₁₀ alkylmono-hydroxyethyl di-methyl quaternary ammonium chloride, mono-C₁₀₋₁₂alkyl mono-hydroxyethyl di-methyl quaternary ammonium chloride andmono-C₁₀ alkyl mono-hydroxyethyl di-methyl quaternary ammonium chloride.

Suitable amphoteric/zwitterionic surfactants include amine oxides andbetaines.

Amine-neutralized anionic surfactants—Anionic surfactants of the presentinvention and adjunct anionic cosurfactants, may exist in an acid form,and said acid form may be neutralized to form a surfactant salt which isdesirable for use in the present detergent compositions. Typical agentsfor neutralization include the metal counterion base such as hydroxides,e.g., NaOH or KOH. Further preferred agents for neutralizing anionicsurfactants of the present invention and adjunct anionic surfactants orcosurfactants in their acid forms include ammonia, amines, oralkanolamines. Alkanolamines are preferred. Suitable non-limitingexamples including monoethanolamine, diethanolamine, triethanolamine,and other linear or branched alkanolamines known in the art; forexample, highly preferred alkanolamines include 2-amino-1-propanol,1-aminopropanol, monoisopropanolamine, or 1-amino-3-propanol. Amineneutralization may be done to a full or partial extent, e.g. part of theanionic surfactant mix may be neutralized with sodium or potassium andpart of the anionic surfactant mix may be neutralized with amines oralkanolamines.

Builders.

Preferably the composition comprises one or more builders or a buildersystem. When a builder is used, the composition of the invention willtypically comprise at least 1%, from 2% to 60% builder. It may bepreferred that the composition comprises low levels of phosphate saltand/or zeolite, for example from 1 to 10 or 5 wt %. The composition mayeven be substantially free of strong builder; substantially free ofstrong builder means “no deliberately added” zeolite and/or phosphate.Typical zeolite builders include zeolite A, zeolite P and zeolite MAP. Atypical phosphate builder is sodium tri-polyphosphate.

Chelating Agent.

Preferably the composition comprises chelating agents and/or crystalgrowth inhibitor. Suitable molecules include copper, iron and/ormanganese chelating agents and mixtures thereof. Suitable moleculesinclude aminocarboxylates, aminophosphonates, succinates, salts thereof,and mixtures thereof. Non-limiting examples of suitable chelants for useherein include ethylenediaminetetracetates,N-(hydroxyethyl)ethylenediaminetriacetates, nitrilotriacetates,ethylenediamine tetraproprionates, triethylenetetraaminehexacetates,diethylenetriamine-pentaacetates, ethanoldiglycines,ethylenediaminetetrakis (methylenephosphonates), diethylenetriaminepenta(methylene phosphonic acid) (DTPMP), ethylenediamine disuccinate(EDDS), hydroxyethanedimethylenephosphonic acid (HEDP),methylglycinediacetic acid (MGDA), diethylenetriaminepentaacetic acid(DTPA), salts thereof, and mixtures thereof. Other nonlimiting examplesof chelants of use in the present invention are found in U.S. Pat. Nos.7,445,644, 7,585,376 and 2009/0176684A1. Other suitable chelating agentsfor use herein are the commercial DEQUEST series, and chelants fromMonsanto, DuPont, and Nalco, Inc.

Dye Transfer Inhibitor (DTI).

The composition may comprise one or more dye transfer inhibiting agents.In one embodiment of the invention the inventors have surprisingly foundthat compositions comprising polymeric dye transfer inhibiting agents inaddition to the specified dye give improved performance. This issurprising because these polymers prevent dye deposition. Suitable dyetransfer inhibitors include, but are not limited to,polyvinylpyrrolidone polymers, polyamine N-oxide polymers, copolymers ofN-vinylpyrrolidone and N-vinylimidazole, polyvinyloxazolidones andpolyvinylimidazoles or mixtures thereof. Suitable examples includePVP-K15, PVP-K30, ChromaBond S-400, ChromaBond S-403E and ChromabondS-100 from Ashland Aqualon, and Sokalan HP165, Sokalan HP50, SokalanHP53, Sokalan HP59, Sokalan® HP 56K, Sokalan® HP 66 from BASF. Othersuitable DTIs are as described in WO2012/004134. When present in asubject composition, the dye transfer inhibiting agents may be presentat levels from about 0.0001% to about 10%, from about 0.01% to about 5%or even from about 0.1% to about 3% by weight of the composition.

Fluorescent Brightener.

Preferably the composition comprises one or more fluorescent brightener.Commercial optical brighteners which may be useful in the presentinvention can be classified into subgroups, which include, but are notlimited to, derivatives of stilbene, pyrazoline, coumarin, carboxylicacid, methinecyanines, dibenzothiophene-5,5-dioxide, azoles, 5- and6-membered-ring heterocycles, and other miscellaneous agents.Particularly preferred brighteners are selected from: sodium 2(4-styryl-3-sulfophenyl)-2H-napthol[1, 2-d]triazole, disodium 4,4′-bis{[(4-anilino-6-(N methyl-N-2 hydroxyethyl) amino 1, 3,5-triazin-2-yl)]amino} stilbene-2-2-disulfonate, disodium 4,4′-bis{[(4-anilino-6-morpholino-I, 3, 5-triazin-2-yl)] amino}stilbene-2-2′ disulfonate, and disodium 4,4′-bis (2-sulfostyryl)biphenyl. Other examples of such brighteners are disclosed in “TheProduction and Application of Fluorescent Brightening Agents”, M.Zahradnik, Published by John Wiley & Sons, New York (1982). Specificnonlimiting examples of optical brighteners which are useful in thepresent compositions are those identified in U.S. Pat. Nos. 4,790,856,and 3,646,015.

A preferred brightener has the structure below:

Suitable fluorescent brightener levels include lower levels of fromabout 0.01, from about 0.05, from about 0.1 or even from about 0.2 wt %to upper levels of 0.5 or even 0.75 wt %.

In one aspect the brightener may be loaded onto a clay to form aparticle.

Preferred brighteners are totally or predominantly (typically at least50 wt %, at least 75 wt %, at least 90 wt %, at least 99 wt %), inalpha-crystalline form. A highly preferred brightener comprises C.I.fluorescent brightener 260, preferably having the following structure:

This can be particularly useful as it dissolves well in cold water, forexample below 30° C. or 25° C. or even 20° C.

Preferably brighteners are incorporated in the composition in micronizedparticulate form, most preferably having a weight average primaryparticle size of from 3 to 30 micrometers, from 3 micrometers to 20micrometers, or from 3 to 10 micrometers.

The composition may comprise C.I. fluorescent brightener 260 inbeta-crystalline form, and the weight ratio of: (i) C.I. fluorescentbrightener 260 in alpha-crystalline form, to (ii) C.I. fluorescentbrightener 260 in beta-crystalline form may be at least 0.1, or at least0.6.

BE680847 relates to a process for making 0.1 fluorescent brightener 260in alpha-crystalline form.

Silicate Salts.

The composition may preferably also contain silicate salts, such assodium or potassium silicate. The composition may comprise from 0 wt %to less than 10 wt % silicate salt, to 9 wt %, or to 8 wt %, or to 7 wt%, or to 6 wt %, or to 5 wt %, or to 4 wt %, or to 3 wt %, or even to 2wt %, and preferably from above 0 wt %, or from 0.5 wt %, or even from 1wt % silicate salt. A suitable silicate salt is sodium silicate.

Dispersants.

The composition may preferably also contain dispersants. Suitablewater-soluble organic materials include the homo- or co-polymeric acidsor their salts, in which the polycarboxylic acid comprises at least twocarboxyl radicals separated from each other by not more than two carbonatoms.

Enzyme Stabilizers.

The composition may preferably comprise enzyme stabilizers. Anyconventional enzyme stabilizer may be used, for example by the presenceof water-soluble sources of calcium and/or magnesium ions in thefinished fabric and home care products that provide such ions to theenzymes. In case of aqueous compositions comprising protease, areversible protease inhibitor, such as a boron compound includingborate, or preferably 4-formyl phenylboronic acid, phenylboronic acidand derivatives thereof, or compounds such as calcium formate, sodiumformate and 1,2-propane diol can be added to further improve stability.

Solvent System.

The solvent system in the present compositions can be a solvent systemcontaining water alone or mixtures of organic solvents either without orpreferably with water. Preferred organic solvents include1,2-propanediol, ethanol, glycerol, dipropylene glycol, methyl propanediol and mixtures thereof. Other lower alcohols, C1-C4 alkanolaminessuch as monoethanolamine and triethanolamine, can also be used. Solventsystems can be absent, for example from anhydrous solid embodiments ofthe invention, but more typically are present at levels in the range offrom about 0.1% to about 98%, preferably at least about 1% to about 50%,more usually from about 5% to about 25%.

In some embodiments of the invention, the composition is in the form ofa structured liquid. Such structured liquids can either be internallystructured, whereby the structure is formed by primary ingredients (e.g.surfactant material) and/or externally structured by providing a threedimensional matrix structure using secondary ingredients (e.g. polymers,clay and/or silicate material), for use e.g. as thickeners. Thecomposition may comprise a structurant, preferably from 0.01 wt % to 5wt %, from 0.1 wt % to 2.0 wt % structurant. Examples of suitablestructurants are given in US2006/0205631A1, US2005/0203213A1, U.S. Pat.Nos. 7,294,611, and 6,855,680. The structurant is typically selectedfrom the group consisting of diglycerides and triglycerides, ethyleneglycol distearate, microcrystalline cellulose, cellulose-basedmaterials, microfiber cellulose, hydrophobically modifiedalkali-swellable emulsions such as Polygel W30 (3VSigma), biopolymers,xanthan gum, gellan gum, hydrogenated castor oil, derivatives ofhydrogenated castor oil such as non-ethoxylated derivatives thereof andmixtures thereof, in particular, those selected from the group ofhydrogenated castor oil, derivatives of hydrogenated castor oil,microfibullar cellulose, hydroxyfunctional crystalline materials, longchain fatty alcohols, 12-hydroxystearic acids, clays and mixturesthereof. A preferred structurant is described in U.S. Pat. No. 6,855,680which defines suitable hydroxyfunctional crystalline materials indetail. Preferred is hydrogenated castor oil. Some structurants have athread-like structuring system having a range of aspect ratios. Othersuitable structurants and the processes for making them are described inWO2010/034736.

The composition of the present invention may comprise a high meltingpoint fatty compound. The high melting point fatty compound usefulherein has a melting point of 25° C. or higher, and is selected from thegroup consisting of fatty alcohols, fatty acids, fatty alcoholderivatives, fatty acid derivatives, and mixtures thereof. Suchcompounds of low melting point are not intended to be included in thissection. Non-limiting examples of the high melting point compounds arefound in International Cosmetic Ingredient Dictionary, Fifth Edition,1993, and CTFA Cosmetic Ingredient Handbook, Second Edition, 1992. Whenpresent, the high melting point fatty compound is preferably included inthe composition at a level of from 0.1% to 40%, preferably from 1% to30%, more preferably from 1.5% to 16% by weight of the composition, from1.5% to 8% in view of providing improved conditioning benefits such asslippery feel during the application to wet hair, softness andmoisturized feel on dry hair.

Cationic Polymer.

The compositions of the present invention may contain a cationicpolymer. Concentrations of the cationic polymer in the compositiontypically range from 0.05% to 3%, in another embodiment from 0.075% to2.0%, and in yet another embodiment from 0.1% to 1.0%. Suitable cationicpolymers will have cationic charge densities of at least 0.5 meq/gm, inanother embodiment at least 0.9 meq/gm, in another embodiment at least1.2 meq/gm, in yet another embodiment at least 1.5 meq/gm, but in oneembodiment also less than 7 meq/gm, and in another embodiment less than5 meq/gm, at the pH of intended use of the composition, which pH willgenerally range from pH 3 to pH 9, in one embodiment between pH 4 and pH8. Herein, “cationic charge density” of a polymer refers to the ratio ofthe number of positive charges on the polymer to the molecular weight ofthe polymer. The average molecular weight of such suitable cationicpolymers will generally be between 10,000 and 10 million, in oneembodiment between 50,000 and 5 million, and in another embodimentbetween 100,000 and 3 million.

Suitable cationic polymers for use in the compositions of the presentinvention contain cationic nitrogen-containing moieties such asquaternary ammonium or cationic protonated amino moieties. Any anioniccounterions can be used in association with the cationic polymers solong as the polymers remain soluble in water, in the composition, or ina coacervate phase of the composition, and so long as the counterionsare physically and chemically compatible with the essential componentsof the composition or do not otherwise unduly impair productperformance, stability or aesthetics. Nonlimiting examples of suchcounterions include halides (e.g., chloride, fluoride, bromide, iodide),sulfate and methylsulfate.

Nonlimiting examples of such polymers are described in the CTFA CosmeticIngredient Dictionary, 3rd edition, edited by Estrin, Crosley, andHaynes, (The Cosmetic, Toiletry, and Fragrance Association, Inc.,Washington, D.C. (1982)).

Other suitable cationic polymers for use in the composition includepolysaccharide polymers, cationic guar gum derivatives, quaternarynitrogen-containing cellulose ethers, synthetic polymers, copolymers ofetherified cellulose, guar and starch. When used, the cationic polymersherein are either soluble in the composition or are soluble in a complexcoacervate phase in the composition formed by the cationic polymer andthe anionic, amphoteric and/or zwitterionic surfactant componentdescribed hereinbefore. Complex coacervates of the cationic polymer canalso be formed with other charged materials in the composition.

Suitable cationic polymers are described in U.S. Pat. Nos. 3,962,418;3,958,581; and U.S. Publication No. 2007/0207109A1.

Nonionic Polymer.

The composition of the present invention may include a nonionic polymeras a conditioning agent. Polyalkylene glycols having a molecular weightof more than 1000 are useful herein. Useful are those having thefollowing general formula:

wherein R⁹⁵ is selected from the group consisting of H, methyl, andmixtures thereof. Conditioning agents, and in particular silicones, maybe included in the composition. The conditioning agents useful in thecompositions of the present invention typically comprise a waterinsoluble, water dispersible, non-volatile, liquid that formsemulsified, liquid particles. Suitable conditioning agents for use inthe composition are those conditioning agents characterized generally assilicones (e.g., silicone oils, cationic silicones, silicone gums, highrefractive silicones, and silicone resins), organic conditioning oils(e.g., hydrocarbon oils, polyolefins, and fatty esters) or combinationsthereof, or those conditioning agents which otherwise form liquid,dispersed particles in the aqueous surfactant matrix herein. Suchconditioning agents should be physically and chemically compatible withthe essential components of the composition, and should not otherwiseunduly impair product stability, aesthetics or performance.

The concentration of the conditioning agent in the composition should besufficient to provide the desired conditioning benefits. Suchconcentration can vary with the conditioning agent, the conditioningperformance desired, the average size of the conditioning agentparticles, the type and concentration of other components, and otherlike factors.

The concentration of the silicone conditioning agent typically rangesfrom about 0.01% to about 10%. Non-limiting examples of suitablesilicone conditioning agents, and optional suspending agents for thesilicone, are described in U.S. Reissue Pat. No. 34,584, U.S. Pat. Nos.5,104,646; 5,106,609; 4,152,416; 2,826,551; 3,964,500; 4,364,837;6,607,717; 6,482,969; 5,807,956; 5,981,681; 6,207,782; 7,465,439;7,041,767; 7,217,777; US Patent Application Nos. 2007/0286837A1;2005/0048549A1; 2007/0041929A1; British Pat. No. 849,433; German PatentNo. DE 10036533, which are all incorporated herein by reference;Chemistry and Technology of Silicones, New York: Academic Press (1968);General Electric Silicone Rubber Product Data Sheets SE 30, SE 33, SE 54and SE 76; Silicon Compounds, Petrarch Systems, Inc. (1984); and inEncyclopedia of Polymer Science and Engineering, vol. 15, 2d ed., pp204-308, John Wiley & Sons, Inc. (1989).

Organic Conditioning Oil.

The compositions of the present invention may also comprise from about0.05% to about 3% of at least one organic conditioning oil as theconditioning agent, either alone or in combination with otherconditioning agents, such as the silicones (described herein). Suitableconditioning oils include hydrocarbon oils, polyolefins, and fattyesters. Also suitable for use in the compositions herein are theconditioning agents described by the Procter & Gamble Company in U.S.Pat. Nos. 5,674,478, and 5,750,122. Also suitable for use herein arethose conditioning agents described in U.S. Pat. Nos. 4,529,586,4,507,280, 4,663,158, 4,197,865, 4,217, 914, 4,381,919, and 4,422, 853.

Hygiene Agent.

The compositions of the present invention may also comprise componentsto deliver hygiene and/or malodour benefits such as one or more of zincricinoleate, thymol, quaternary ammonium salts such as Bardac®,polyethyleneimines (such as Lupasol® from BASF) and zinc complexesthereof, silver and silver compounds, especially those designed toslowly release Ag+ or nano-silver dispersions.

Probiotics.

The composition may comprise probiotics, such as those described inWO2009/043709.

Suds Boosters.

The composition may preferably comprise suds boosters if high sudsing isdesired. Suitable examples are the C₁₀-C₁₆ alkanolamides or C₁₀-C₁₄alkyl sulphates, which are preferably incorporated at 1%-10% levels. TheC₁₀-C₁₄ monoethanol and diethanol amides illustrate a typical class ofsuch suds boosters. Use of such suds boosters with high sudsing adjunctsurfactants such as the amine oxides, betaines and sultaines noted aboveis also advantageous. If desired, water-soluble magnesium and/or calciumsalts such as MgCl₂, MgSO₄, CaCl₂, CaSO₄ and the like, can be added atlevels of, typically, 0.1%-2%, to provide additional suds and to enhancegrease removal performance.

Suds Suppressor.

Compounds for reducing or suppressing the formation of suds may beincorporated into the compositions of the present invention. Sudssuppression can be of particular importance in the so-called “highconcentration cleaning process” as described in U.S. Pat. Nos. 4,489,455and 4,489,574, and in front-loading-style washing machines. A widevariety of materials may be used as suds suppressors, and sudssuppressors are well known to those skilled in the art. See, forexample, Kirk Othmer Encyclopedia of Chemical Technology, Third Edition,Volume 7, pages 430-447 (John Wiley & Sons, Inc., 1979). Examples ofsuds suppressors include monocarboxylic fatty acid and soluble saltstherein, high molecular weight hydrocarbons such as paraffin, fatty acidesters (e.g., fatty acid triglycerides), fatty acid esters of monovalentalcohols, aliphatic C18-C40 ketones (e.g., stearone), N-alkylated aminotriazines, waxy hydrocarbons preferably having a melting point belowabout 100° C., silicone suds suppressors, and secondary alcohols. Sudssuppressors are described in U.S. Pat. Nos. 2,954,347; 4,265,779;4,265,779; 3,455,839; 3,933,672; 4,652,392; 4,978,471; 4,983,316;5,288,431; 4,639,489; 4,749,740; and 4,798,679; 4,075,118; EuropeanPatent Application No. 89307851.9; EP 150,872; and DOS 2,124,526.

For any detergent compositions to be used in automatic laundry washingmachines, suds should not form to the extent that they overflow thewashing machine. Suds suppressors, when utilized, are preferably presentin a suds suppressing amount. “Suds suppressing amount” is meant thatthe formulator of the composition can select an amount of this sudscontrolling agent that will sufficiently control the suds to result in alow-sudsing laundry detergent for use in automatic laundry washingmachines. The compositions herein will generally comprise from 0% to 10%of suds suppressor. When utilized as suds suppressors, monocarboxylicfatty acids, and salts therein, will be present typically in amounts upto 5%, by weight, of the detergent composition. Preferably, from 0.5% to3% of fatty monocarboxylate suds suppressor is utilized. Silicone sudssuppressors are typically utilized in amounts up to 2.0%, by weight, ofthe detergent composition, although higher amounts may be used.Monostearyl phosphate suds suppressors are generally utilized in amountsranging from 0.1% to 2%, by weight, of the composition. Hydrocarbon sudssuppressors are typically utilized in amounts ranging from 0.01% to5.0%, although higher levels can be used. The alcohol suds suppressorsare typically used at 0.2%-3% by weight of the finished compositions.

Pearlescent Agents.

Pearlescent agents as described in WO2011/163457 may be incorporatedinto the compositions of the invention.

The pearlescent agents can be crystalline or glassy solids, transparentor translucent compounds capable of reflecting and refracting light toproduce a pearlescent effect. Typically, the pearlescent agents arecrystalline particles insoluble in the composition in which they areincorporated. Preferably the pearlescent agents have the shape of thinplates or spheres. Particle size is measured across the largest diameterof the sphere-like particle. Plate-like particles are such that twodimensions of the particle (length and width) are at least 5 times thethird dimension (depth or thickness). Other crystal shapes like cubes orneedles or other crystal shapes do not display pearlescent effect. Manypearlescent agents like mica are natural minerals having monocliniccrystals. Shape appears to affect the stability of the agents. Thespherical, even more preferably, the plate-like agents being the mostsuccessfully stabilized. Particle size of the pearlescent agent istypically below 200 microns, preferably below 100 microns, morepreferably below 50 microns.

In one preferred embodiment, the particles are randomly orientedthroughout the liquid so that they scatter light from incoming angles,giving a constant pearlescent look independent of the angle from whichthe sample is observed. Alternatively, particles could also be orderedin the same direction to obtain a different light scattering profile andtherefore provide a look dependent upon the angle through which thesample is observed.

The compositions may comprise from 0.005% to 3.0% wt, preferably from0.01% to 1%, by weight of the composition of the 100% active pearlescentagents. The pearlescent agents may be organic or inorganic. Thecomposition can comprise organic and/or inorganic pearlescent agent.

Organic Pearlescent Agents:

When the composition comprises an organic pearlescent agent, it iscomprised at an active level of from 0.05% to 2.0% wt, preferably from0.1% to 1.0% by weight of the composition of the 100% active organicpearlescent agents. Suitable organic pearlescent agents includemonoester and/or diester of alkylene glycols having the formula:

wherein R₁ is linear or branched C12-C22 alkyl group;R is linear or branched C2-C4 alkylene group;P is selected from H, C1-C4 alkyl or —COR₂, R₂ is C4-C22 alkyl,preferably C12-C22 alkyl; andn=1-3.

In one embodiment, the long chain fatty ester has the general structuredescribed above, wherein R₁ is linear or branched C16-C22 alkyl group, Ris —CH₂—CH₂—, and P is selected from H, or —COR₂, wherein R₂ is C4-C22alkyl, preferably C12-C22 alkyl.

Typical examples are monoesters and/or diesters of ethylene glycol,propylene glycol, diethylene glycol, dipropylene glycol, triethyleneglycol or tetraethylene glycol with fatty acids containing from about 6to about 22, preferably from about 12 to about 18 carbon atoms, such ascaproic acid, caprylic acid, 2-ethyhexanoic acid, capric acid, lauricacid, isotridecanoic acid, myristic acid, palmitic acid, palmitoleicacid, stearic acid, isostearic acid, oleic acid, elaidic acid,petroselic acid, linoleic acid, linolenic acid, arachic acid, gadoleicacid, behenic acid, erucic acid, and mixtures thereof.

In one embodiment, ethylene glycol monostearate (EGMS) and/or ethyleneglycol distearate (EGDS) and/or polyethylene glycol monostearate (PGMS)and/or polyethyleneglycol distearate (PGDS) are the pearlescent agentsused in the composition. There are several commercial sources for thesematerials. For example, PEG6000MS® is available from Stepan, EmpilanEGDS/A® is available from Albright & Wilson.

In another embodiment, the pearlescent agent comprises a mixture ofethylene glycol diester/ethylene glycol monoester having the weightratio of about 1:2 to about 2:1. In another embodiment, the pearlescentagent comprising a mixture of EGDS/EGMS having the weight ratio of about60:40 to about 50:50 is found to be particularly stable in watersuspension.

Co-Crystallizing Agents:

Optionally, co-crystallizing agents are used to enhance thecrystallization of the organic pearlescent agents such that pearlescentparticles are produced in the resulting product. Suitableco-crystallizing agents include but are not limited to fatty acidsand/or fatty alcohols having a linear or branched, optionally hydroxylsubstituted, alkyl group containing from about 12 to about 22,preferably from about 16 to about 22, and more preferably from about 18to 20 carbon atoms, such as palmitic acid, linoleic acid, stearic acid,oleic acid, ricinoleic acid, behenyl acid, cetearyl alcohol,hydroxystearyl alcohol, behenyl alcohol, linolyl alcohol, linolenylalcohol, and mixtures thereof. In one embodiment where theco-crystallizing agent is present, the composition comprises 1-5 wt %C12-C20 fatty acid, C12-C20 fatty alcohol, or mixtures thereof. Inanother embodiment, the weight ratio between the organic pearlescentagent and the co-crystallizing agent ranges from about 3:1 to about10:1, or from about 5:1 to about 20:1. A preferred method ofincorporating organic pearlescent agents into a composition is to use apre-crystallized organic pearlescent dispersion, named as “cold pearl”.A number of cold pearls are commercially available. These include tradenames such as Stepan, Pearl-2 and Stepan Pearl 4 (produced by StepanCompany Northfield, Ill.), Mackpearl 202, Mackpearl 15-DS, MackpearlDR-104, Mackpearl DR-106 (all produced by McIntyre Group, Chicago,Ill.), Euperlan PK900 Benz-W and Euperlan PK 3000 AM (produced by CognisCorp).

Inorganic Pearlescent Agents:

In another embodiment the composition might also comprise an inorganicpearlescent agent. When the composition comprises an inorganicpearlescent agent, it is comprised at an active level of from 0.005% to1.0% wt, preferably from 0.01% to 0.2% by weight of the composition ofthe 100% active inorganic pearlescent agents.

Inorganic pearlescent agents include aluminosilicates and/orborosilicates. Preferred are the aluminosilicates and/or borosilicateswhich have been treated to have a very high refractive index, preferablysilica, metal oxides, oxychloride coated aluminosilicate and/orborosilicates. More preferred inorganic pearlescent agent is mica, evenmore preferred titanium dioxide treated mica such as BASF MearlinSuperfine.

It is preferable to use a pearlescent pigment with a high refractiveindex in order to keep the level of pigment at a reasonably low level inthe formulation. Hence the pearlescent agent is preferably chosen suchthat it has a refractive index of more than 1.41, more preferably morethan 1.8, even more preferably more than 2.0. Preferably the differencein refractive index between the pearlescent agent and the composition ormedium, to which pearlescent agent is then added, is at least 0.02.Preferably the difference in refractive index between the pearlescentagent and the composition is at least 0.2, more preferably at least 0.6.

One preferred embodiment is metal oxide treated mica such as titaniumoxide treated mica with a titanium oxide thickness from 1 nm to 150 nm,preferentially from 2 to 100 more preferentially from 5 to 50 nm toproduce a silvery iridescence or from 50 nm to 150 nm produce colorsthat appear bronze, copper, red, red-violet or red-green. Goldiridescence could be obtained by applying a layer of iron oxide on topof a layer of titanium oxide. Typical interference pigment function ofthe thickness of the metal oxide layer could be found in scientificliterature.

Other commercially available suitable inorganic pearlescent agents areavailable from Merck under the tradenames Iriodin, Biron, Xirona,Timiron Colorona, Dichrona, Candurin and Ronastar. Other commerciallyavailable inorganic pearlescent agent are available from BASF(Engelhard, Mearl) under tradenames Biju, Bi-Lite, Chroma-Lite,Pearl-Glo, Mearlite and from Eckart under the tradenames Prestige SoftSilver and Prestige Silk Silver Star.

Suspension Particles

In one embodiment, the composition further comprises a plurality ofsuspension particles at a level of from about 0.01% to about 5% byweight, alternatively from about 0.05% to about 4% by weight,alternatively from about 0.1% to about 3% by weight. Examples ofsuitable suspension particles are provided in U.S. Pat. No. 7,169,741and U.S. Patent Publ. No. 2005/0203213, the disclosures of which areincorporated herein by reference. These suspended particles can comprisea liquid core or a solid core. Detailed description of these liquid coreand solid core particles, as well as description of preferred particlesize, particle shape, particle density, and particle burst strength aredescribed in U.S. patent application Ser. No. 12/370,714, the disclosureof which is incorporated herein by reference.

In one preferred embodiment, the particles may be any discrete andvisually distinguishable form of matter, including but not limiting to(deformable) beads, encapsulates, polymeric particles like plastic,metals (e.g. foil material, flakes, glitter), (interference) pigments,minerals (salts, rocks, pebbles, lava, glass/silica particles, talc),plant materials (e.g. pits or seeds, plant fibers, stalks, stems, leavesor roots), solid and liquid crystals, and the like. Different particleshapes are possible, ranging from spherical to tabular.

In one embodiment, the suspension particles may be gas or air bubbles.In this embodiment, the diameter of each bubble may be from about 50 toabout 2000 microns and may be present at a level of about 0.01 to about5% by volume of the composition alternatively from about 0.05% to about4% by volume of the composition, alternatively from about 0.1% to about3% by volume of the composition.

Many different techniques have been devised for determining particlesize distribution in compositions, but for a wide range of industrieslaser based analytical method diffraction has become the preferredchoice. For example, laser diffraction, alternatively referred to as LowAngle Laser Light Scattering (LALLS), can be used for thenon-destructive analysis of wet or dry samples, with particles in thesize range 0.02 to 2000 micron. Alternatively online droplet sizingsystems capture high-speed images of bubble stream to give the dropsize. In addition to measuring the particle diameter distribution,lasers imaging systems also provide real-time shape and velocityanalysis.

Laser diffraction based particle size analysis relies on the fact thatparticles passing through a laser beam will scatter light at an anglethat is directly related to their size. As particle size decreases, theobserved scattering angle increases logarithmically. Scatteringintensity is also dependent on particle size, diminishing with particlevolume. Large particles therefore scatter light at narrow angles withhigh intensity whereas small particles scatter at wider angles but withlow intensity. It is this behavior that instruments based on thetechnique of laser diffraction exploit in order to determine particlesize. A typical system consists of a laser, to provide a source ofcoherent, intense light of fixed wavelength; a series of detectors tomeasure the light pattern produced over a wide range of angles; and somekind of sample presentation system to ensure that material under testpasses through the laser beam as a homogeneous stream of particles in aknown, reproducible state of dispersion.

Perfume Microcapsules

In one embodiment, the composition comprises a perfume microcapsuleand/or a perfume nanocapsule. Suitable perfume microcapsules and perfumenanocapsules include those described in the following references: US2003215417 A1; US 2003216488 A1; US 2003158344 A1; US 2003165692 A1; US2004071742 A1; US 2004071746 A1; US 2004072719 A1; US 2004072720 A1; EP1393706 A1; US 2003203829 A1; US 2003195133 A1; US 2004087477 A1; US20040106536 A1; U.S. Pat. Nos. 6,645,479; 6,200,949; 4,882,220;4,917,920; 4,514,461; US RE 32713; U.S. Pat. No. 4,234,627, thedisclosures of which are incorporated herein by reference.

In yet another embodiment, the composition comprises odor control agentssuch as described in U.S. Pat. No. 5,942,217: “Uncomplexed cyclodextrincompositions for odor control”, granted Aug. 24, 1999. Other agentssuitable odor control agents include those described in: U.S. Pat. Nos.5,968,404, 5,955,093; 6,106,738; 5,942,217; and 6,033,679, thedisclosures of which are incorporated herein by reference.

Opacifier

In one embodiment, the composition might also comprise an opacifier.

As the term is used herein, an “opacifier” is a substance added to amaterial in order to make the ensuing system opaque. In one preferredembodiment, the opacifier is Acusol, which is available from DowChemicals. Acusol opacifiers are provided in liquid form at a certain %solids level. As supplied, the pH of Acusol opacifiers ranges from 2.0to 5.0 and particle sizes range from 0.17 to 0.45 um. In one preferredembodiment, Acusol OP303B and 301 can be used.

In yet another embodiment, the opacifier may be an inorganic opacifier.Preferably, the inorganic opacifier can be TiO₂, ZnO, talc, CaCO₃, andcombination thereof. The composite opacifier-microsphere material isreadily formed with a preselected specific gravity, so that there islittle tendency for the material to separate.

Organic Solvents

The compositions may optionally comprise an organic solvent. Suitableorganic solvents include C₄₋₁₄ ethers and diethers, glycols, alkoxylatedglycols, C₆-C₁₆ glycol ethers, alkoxylated aromatic alcohols, aromaticalcohols, aliphatic branched alcohols, alkoxylated aliphatic branchedalcohols, alkoxylated linear C₁-C₅ alcohols, linear C₁-C₅ alcohols,amines, C₈-C₁₄ alkyl and cycloalkyl hydrocarbons and halohydrocarbons,and mixtures thereof. In one embodiment, the liquid detergentcomposition comprises from about 0.0% to less than 50% of a solvent.When present, the liquid detergent composition will contain from about0.01% to about 20%, alternatively from about 0.5% to about 15%,alternatively from about 1% to about 10% by weight of the liquiddetergent composition of said organic solvent. These organic solventsmay be used in conjunction with water, or they may be used withoutwater.

Hydrotrope

The composition may optionally comprises a hydrotrope in an effectiveamount, i.e. from about 0% to 15%, or about 1% to 10%, or about 3% toabout 6%, so that compositions are compatible in water. Suitablehydrotropes for use herein include anionic-type hydrotropes,particularly sodium, potassium, and ammonium xylene sulfonate, sodium,potassium and ammonium toluene sulfonate, sodium potassium and ammoniumcumene sulfonate, and mixtures thereof, as disclosed in U.S. Pat. No.3,915,903.

Polymeric Suds Stabilizer

The composition may optionally contain a polymeric suds stabilizer at alevel from about 0.01% to about 15%. These polymeric suds stabilizersprovide extended suds volume and suds duration of the liquid detergentcompositions. These polymeric suds stabilizers may be selected fromhomopolymers of (N,N-dialkylamino) alkyl esters and (N,N-dialkylamino)alkyl acrylate esters. The weight average molecular weight of thepolymeric suds boosters, determined via conventional gel permeationchromatography, is from about 1,000 to about 2,000,000, alternativelyfrom about 5,000 to about 1,000,000, alternatively from about 10,000 toabout 750,000, alternatively from about 20,000 to about 500,000,alternatively from about 35,000 to about 200,000. The polymeric sudsstabilizer can optionally be present in the form of a salt, either aninorganic or organic salt, for example the citrate, sulfate, or nitratesalt of (N,N-dimethylamino)alkyl acrylate ester.

One suitable polymeric suds stabilizer is (N,N-dimethylamino)alkylacrylate esters, namely the acrylate ester represented by the followingformula:

When present in the compositions, the polymeric suds booster may bepresent in the composition from about 0.01% to about 15%, alternativelyfrom about 0.05% to about 10%, alternatively from about 0.1% to about5%, by weight of the composition.

Anti-Oxidant

The composition may optionally contain an anti-oxidant present in thecomposition from about 0.001 to about 2% by weight. Preferably theantioxidant is present at a concentration in the range 0.01 to 0.08% byweight.

Anti-oxidants are substances as described in Kirk-Othmer (Vol. 3, page424) and In Ullmann's Encyclopedia (Vol. 3, page 91).

One class of anti-oxidants used in the present invention is alkylatedphenols, having the general formula:

wherein R is C₁-C₂₂ linear or branched alkyl, preferably methyl orbranched C₃-C₆ alkyl, C₃-C₆ alkoxy, preferably methoxy; R₁ is a C₃-C₆branched alkyl, preferably tert-butyl; x is 1 or 2. Hindered phenoliccompounds are a preferred type of alkylated phenols having this formula.A preferred hindered phenolic compound of this type is2,6-di-tert-butylhydroxytoluene (BHT).

Furthermore, the anti-oxidant used in the composition may be selectedfrom the group consisting of α-, β-, γ-, δ-tocopherol, ethoxyquin,2,2,4-trimethyl-1,2-dihydroquinoline, 2,6-di-tert-butyl hydroquinone,tert-butyl hydroxyanisole, lignosulphonic acid and salts thereof, andmixtures thereof. It is noted that ethoxyquin(1,2-dihydro-6-ethoxy-2,2,4-trimethylquinoline) is marketed under thename Raluquin™ by the company Raschig™.

Other types of anti-oxidants that may be used in the composition are6-hydroxy-2,5,7,8-tetramethylchroman-2-carboxylic acid (Trolox™) and1,2-benzisothiazoline-3-one (Proxel GXL™).

A further class of anti-oxidants which may be suitable for use in thecomposition is a benzofuran or benzopyran derivative having the formula:

wherein R₁ and R₂ are each independently alkyl or R₁ and R₂ can be takentogether to form a C₅-C₆ cyclic hydrocarbyl moiety; B is absent or CH₂;R₄ is C₁-C₆ alkyl; R₅ is hydrogen or —C(O)R₃ wherein R₃ is hydrogen orC₁-C₁₉ alkyl; R₆ is C₁-C₆ alkyl; R₇ is hydrogen or C₁-C₆ alkyl; X is—CH₂OH, or —CH₂A wherein A is a nitrogen comprising unit, phenyl, orsubstituted phenyl. Preferred nitrogen comprising A units include amino,pyrrolidino, piperidino, morpholino, piperazino, and mixtures thereof.

Anti-oxidants such as tocopherol sorbate, butylated hydroxyl benxoicacids and their salts, gallic acid and its alkyl esters, uric acid andits salts, sorbic acid and its salts, and dihydroxyfumaric acid and itssalts may also be used. The most preferred types of anti-oxidant for usein the composition are 2,6-di-tert-butylhydroxytoluene (BHT), α-, β-,γ-, δ-tocopherol, 1,2-benzisothiazoline-3-one (Proxel GXL™) and mixturesthereof.

Perfume.

Preferably the composition comprises a perfume, preferably in the rangefrom 0.001 to 3 wt %, most preferably from 0.1 to 1 wt %. Many suitableexamples of perfumes are provided in the CTFA (Cosmetic, Toiletry andFragrance Association) 1992 International Buyers Guide, published byCFTA Publications and OPD 1993 Chemicals Buyers Directory 80^(th) AnnualEdition, published by Schnell Publishing Co. It is usual for a pluralityof perfume components to be present in the compositions of theinvention, for example four, five, six, seven or more. In perfumemixtures preferably 15 to 25 wt % are top notes. Top notes are definedby Poucher (Journal of the Society of Cosmetic Chemists 6(2):80 [1995]).Preferred top notes include rose oxide, citrus oils, linalyl acetate,lavender, linalool, dihydromyrcenol and cis-3-hexanol.

Packaging.

Any conventional packaging may be used and the packaging may be fully orpartially transparent so that the consumer can see the color of theproduct which may be provided or contributed to by the color of the dyesessential to the invention. UV absorbing compounds may be included insome or all of the packaging.

Process of Making Compositions

The compositions of the invention may be in any useful form, asdescribed above. They may be made by any process chosen by theformulator, non-limiting examples of which are described in the examplesand in U.S. Pat. No. 4,990,280; U.S. 20030087791A1; U.S. 20030087790A1;U.S. 20050003983A1; U.S. 20040048764A1; U.S. Pat. Nos. 4,762,636;6,291,412; U.S. 20050227891A1; EP 1070115A2; U.S. Pat. No. 5,879,584;U.S. Pat. Nos. 5,691,297; 5,574,005; 5,569,645; 5,565,422; 5,516,448;5,489,392; U.S. 5,486.

When in the form of a liquid, the laundry care compositions of theinvention may be aqueous (typically above 2 wt % or even above 5 or 10wt % total water, up to 90 or up to 80 wt % or 70 wt % total water) ornon-aqueous (typically below 2 wt % total water content). Typically thecompositions of the invention will be in the form of an aqueous solutionor uniform dispersion or suspension of surfactant, shading dye, andcertain optional other ingredients, some of which may normally be insolid form, that have been combined with the normally liquid componentsof the composition, such as the liquid alcohol ethoxylate nonionic, theaqueous liquid carrier, and any other normally liquid optionalingredients. Such a solution, dispersion or suspension will beacceptably phase stable. When in the form of a liquid, the laundry carecompositions of the invention preferably have viscosity from 1 to 1500centipoises (1-1500 mPa*s), more preferably from 100 to 1000 centipoises(100-1000 mPa*s), and most preferably from 200 to 500 centipoises(200-500 mPa*s) at 20s−1 and 21° C. Viscosity can be determined byconventional methods. Viscosity may be measured using an AR 550rheometer from TA instruments using a plate steel spindle at 40 mmdiameter and a gap size of 500 μm. The high shear viscosity at 20s−1 andlow shear viscosity at 0.05-1 can be obtained from a logarithmic shearrate sweep from 0.1-1 to 25-1 in 3 minutes time at 21° C. The preferredrheology described therein may be achieved using internal existingstructuring with detergent ingredients or by employing an externalrheology modifier. More preferably the laundry care compositions, suchas detergent liquid compositions have a high shear rate viscosity offrom about 100 centipoise to 1500 centipoise, more preferably from 100to 1000 cps. Unit Dose laundry care compositions, such as detergentliquid compositions have high shear rate viscosity of from 400 to 1000cps. Laundry care compositions such as laundry softening compositionstypically have high shear rate viscosity of from 10 to 1000, morepreferably from 10 to 800 cps, most preferably from 10 to 500 cps. Handdishwashing compositions have high shear rate viscosity of from 300 to4000 cps, more preferably 300 to 1000 cps.

The liquid compositions, preferably liquid detergent compositions hereincan be prepared by combining the components thereof in any convenientorder and by mixing, e.g., agitating, the resulting componentcombination to form a phase stable liquid detergent composition. In aprocess for preparing such compositions, a liquid matrix is formedcontaining at least a major proportion, or even substantially all, ofthe liquid components, e.g., nonionic surfactant, the non-surface activeliquid carriers and other optional liquid components, with the liquidcomponents being thoroughly admixed by imparting shear agitation to thisliquid combination. For example, rapid stirring with a mechanicalstirrer may usefully be employed. While shear agitation is maintained,substantially all of any anionic surfactants and the solid formingredients can be added. Agitation of the mixture is continued, and ifnecessary, can be increased at this point to form a solution or auniform dispersion of insoluble solid phase particulates within theliquid phase. After some or all of the solid-form materials have beenadded to this agitated mixture, particles of any enzyme material to beincluded, e.g., enzyme prills, are incorporated. As a variation of thecomposition preparation procedure hereinbefore described, one or more ofthe solid components may be added to the agitated mixture as a solutionor slurry of particles premixed with a minor portion of one or more ofthe liquid components. After addition of all of the compositioncomponents, agitation of the mixture is continued for a period of timesufficient to form compositions having the requisite viscosity and phasestability characteristics. Frequently this will involve agitation for aperiod of from about 30 to 60 minutes.

In one aspect of forming the liquid compositions, the dye is firstcombined with one or more liquid components to form a dye premix, andthis dye premix is added to a composition formulation containing asubstantial portion, for example more than 50% by weight, morespecifically, more than 70% by weight, and yet more specifically, morethan 90% by weight, of the balance of components of the laundrydetergent composition. For example, in the methodology described above,both the dye premix and the enzyme component are added at a final stageof component additions. In another aspect, the dye is encapsulated priorto addition to the detergent composition, the encapsulated dye issuspended in a structured liquid, and the suspension is added to acomposition formulation containing a substantial portion of the balanceof components of the laundry detergent composition.

The leuco colorants of the present invention have been found to besuitable for use in liquid laundry care compositions having a wide rangeof pH values. For example, the inventive leuco colorants have been foundto be suitable for use in liquid laundry care compositions having a pHof greater than or equal to 10. The inventive leuco colorants have alsobeen found to be suitable for use in liquid laundry care compositionshaving a pH of less than 10. Thus, the leuco colorant are stable inlaundry care compositions having pH values of greater than or equal to10 and less than or equal to 10.

Pouches.

In a preferred embodiment of the invention, the composition is providedin the form of a unitized dose, either tablet form or preferably in theform of a liquid/solid (optionally granules)/gel/paste held within awater-soluble film in what is known as a pouch or pod. The compositioncan be encapsulated in a single or multi-compartment pouch.Multi-compartment pouches are described in more detail in EP-A-2133410.When the composition is present in a multi-compartment pouch, thecomposition of the invention may be in one or two or more compartments,thus the dye may be present in one or more compartments, optionally allcompartments. Non-shading dyes or pigments or other aesthetics may alsobe used in one or more compartments. In one embodiment the compositionis present in a single compartment of a multi-compartment pouch.

Suitable film for forming the pouches is soluble or dispersible inwater, and preferably has a water-solubility/dispersibility of at least50%, preferably at least 75% or even at least 95%, as measured by themethod set out here after using a glass-filter with a maximum pore sizeof 20 microns:

50 grams±0.1 gram of pouch material is added in a pre-weighed 400 mlbeaker and 245 ml±1 ml of distilled water is added. This is stirredvigorously on a magnetic stirrer set at 600 rpm, for 30 minutes. Then,the mixture is filtered through a folded qualitative sintered-glassfilter with a pore size as defined above (max. 20 micron). The water isdried off from the collected filtrate by any conventional method, andthe weight of the remaining material is determined (which is thedissolved or dispersed fraction). Then, the percentage solubility ordispersibility can be calculated. Preferred film materials are polymericmaterials. The film material can be obtained, for example, by casting,blow-molding, extrusion or blown extrusion of the polymeric material, asknown in the art. Preferred polymers, copolymers or derivatives thereofsuitable for use as pouch material are selected from polyvinyl alcohols,polyvinyl pyrrolidone, polyalkylene oxides, acrylamide, acrylic acid,cellulose, cellulose ethers, cellulose esters, cellulose amides,polyvinyl acetates, polycarboxylic acids and salts, polyaminoacids orpeptides, polyamides, polyacrylamide, copolymers of maleic/acrylicacids, polysaccharides including starch and gelatine, natural gums suchas xanthum and carragum. More preferred polymers are selected frompolyacrylates and water-soluble acrylate copolymers, methylcellulose,carboxymethylcellulose sodium, dextrin, ethylcellulose, hydroxyethylcellulose, hydroxypropyl methylcellulose, maltodextrin,polymethacrylates, and most preferably selected from polyvinyl alcohols,polyvinyl alcohol copolymers and hydroxypropyl methyl cellulose (HPMC),and combinations thereof. Preferably, the level of polymer in the pouchmaterial, for example a PVA polymer, is at least 60%. The polymer canhave any weight average molecular weight, preferably from about 1000 to1,000,000, more preferably from about 10,000 to 300,000 yet morepreferably from about 20,000 to 150,000. Mixtures of polymers can alsobe used as the pouch material. This can be beneficial to control themechanical and/or dissolution properties of the compartments or pouch,depending on the application thereof and the required needs. Suitablemixtures include for example mixtures wherein one polymer has a higherwater-solubility than another polymer, and/or one polymer has a highermechanical strength than another polymer. Also suitable are mixtures ofpolymers having different weight average molecular weights, for examplea mixture of PVA or a copolymer thereof of a weight average molecularweight of about 10,000-40,000, preferably around 20,000, and of PVA orcopolymer thereof, with a weight average molecular weight of about100,000 to 300,000, preferably around 150,000. Also suitable herein arepolymer blend compositions, for example comprising hydrolyticallydegradable and water-soluble polymer blends such as polylactide andpolyvinyl alcohol, obtained by mixing polylactide and polyvinyl alcohol,typically comprising about 1-35% by weight polylactide and about 65% to99% by weight polyvinyl alcohol. Preferred for use herein are polymerswhich are from about 60% to about 98% hydrolysed, preferably about 80%to about 90% hydrolysed, to improve the dissolution characteristics ofthe material.

Naturally, different film material and/or films of different thicknessmay be employed in making the compartments of the present invention. Abenefit in selecting different films is that the resulting compartmentsmay exhibit different solubility or release characteristics.

Most preferred film materials are PVA films known under the MonoSoltrade reference M8630, M8900, H8779 and those described in U.S. Pat.Nos. 6,166,117 and 6,787,512 and PVA films of corresponding solubilityand deformability characteristics.

The film material herein can also comprise one or more additiveingredients. For example, it can be beneficial to add plasticizers, forexample glycerol, ethylene glycol, diethyleneglycol, propylene glycol,sorbitol and mixtures thereof. Other additives include functionaldetergent additives to be delivered to the wash water, for exampleorganic polymeric dispersants, etc.

Process for Making the Water-Soluble Pouch

The compositions of the invention in pouch form may be made using anysuitable equipment and method. However the multi-compartment pouches arepreferably made using the horizontal form filling process. The film ispreferably wetting, more preferably heated to increase the malleabilitythereof. Even more preferably, the method also involves the use of avacuum to draw the film into a suitable mold. The vacuum drawing thefilm into the mold can be applied for 0.2 to 5 seconds, preferably 0.3to 3 or even more preferably 0.5 to 1.5 seconds, once the film is on thehorizontal portion of the surface. This vacuum may preferably be suchthat it provides an under-pressure of between −100 mbar to −1000 mbar,or even from −200 mbar to −600 mbar.

The molds, in which the pouches are made, can have any shape, length,width and depth, depending on the required dimensions of the pouches.The molds can also vary in size and shape from one to another, ifdesirable. For example, it may be preferred that the volume of the finalpouches is between 5 and 300 ml, or even 10 and 150 ml or even 20 and100 ml and that the mold sizes are adjusted accordingly.

Heat can be applied to the film, in the process commonly known asthermoforming, by any means. For example the film may be heated directlyby passing it under a heating element or through hot air, prior tofeeding it onto the surface or once on the surface. Alternatively it maybe heated indirectly, for example by heating the surface or applying ahot item onto the film. Most preferably the film is heated using aninfrared light. The film is preferably heated to a temperature of 50 to120° C., or even 60 to 90° C. Alternatively, the film can be wetted byany mean, for example directly by spraying a wetting agent (includingwater, solutions of the film material or plasticizers for the filmmaterial) onto the film, prior to feeding it onto the surface or once onthe surface, or indirectly by wetting the surface or by applying a wetitem onto the film.

In the case of pouches comprising powders it is advantageous to pinprick the film for a number of reasons: (a) to reduce the possibility offilm defects during the pouch formation, for example film defects givingrise to rupture of the film can be generated if the stretching of thefilm is too fast; (b) to permit the release of any gases derived fromthe product enclosed in the pouch, as for example oxygen formation inthe case of powders containing bleach; and/or (c) to allow thecontinuous release of perfume. Moreover, when heat and/or wetting isused, pin pricking can be used before, during or after the use of thevacuum, preferably during or before application of the vacuum. Preferredis thus that each mold comprises one or more holes which are connectedto a system which can provide a vacuum through these holes, onto thefilm above the holes, as described herein in more detail.

Once a film has been heated/wetted, it is drawn into an appropriatemold, preferably using a vacuum. The filling of the molded film can bedone by any known method for filling (moving) items. The most preferredmethod will depend on the product form and speed of filling required.Preferably the molded film is filled by in-line filling techniques. Thefilled, open pouches are then closed, using a second film, by anysuitable method. Preferably, this is also done while in horizontalposition and in continuous, constant motion. Preferably the closing isdone by continuously feeding a second material or film, preferablywater-soluble film, over and onto the web of open pouches and thenpreferably sealing the first film and second film together, typically inthe area between the molds and thus between the pouches.

Preferred methods of sealing include heat sealing, solvent welding, andsolvent or wet sealing. It is preferred that only the area which is toform the seal, is treated with heat or solvent. The heat or solvent canbe applied by any method, preferably on the closing material, preferablyonly on the areas which are to form the seal. If solvent or wet sealingor welding is used, it may be preferred that heat is also applied.Preferred wet or solvent sealing/welding methods include applyingselectively solvent onto the area between the molds, or on the closingmaterial, by for example, spraying or printing this onto these areas,and then applying pressure onto these areas, to form the seal. Sealingrolls and belts as described above (optionally also providing heat) canbe used, for example.

The formed pouches can then be cut by a cutting device. Cutting can bedone using any known method. It may be preferred that the cutting isalso done in continuous manner, and preferably with constant speed andpreferably while in horizontal position. The cutting device can, forexample, be a sharp item or a hot item, whereby in the latter case, thehot item ‘burns’ through the film/sealing area.

The different compartments of a multi-compartment pouch may be madetogether in a side-by-side style and consecutive pouches are not cut.Alternatively, the compartments can be made separately. According tothis process and preferred arrangement, the pouches are made accordingto the process comprising the steps of:

a) forming an first compartment (as described above);

b) forming a recess within some or all of the closed compartment formedin step (a), to generate a second molded compartment superposed abovethe first compartment;

c) filling and closing the second compartments by means of a third film;

d) sealing said first, second and third films; and

e) cutting the films to produce a multi-compartment pouch.

Said recess formed in step b is preferably achieved by applying a vacuumto the compartment prepared in step a).

Alternatively the second, and optionally third, compartment(s) can bemade in a separate step and then combined with the first compartment asdescribed in EP 08101442.5 which is incorporated herein by reference. Aparticularly preferred process comprises the steps of:

a) forming a first compartment, optionally using heat and/or vacuum,using a first film on a first forming machine;

b) filling said first compartment with a first composition;

c) on a second forming machine, deforming a second film, optionallyusing heat and vacuum, to make a second and optionally third moldedcompartment;

d) filling the second and optionally third compartments;

e) sealing the second and optionally third compartment using a thirdfilm;

f) placing the sealed second and optionally third compartments onto thefirst compartment;

g) sealing the first, second and optionally third compartments; and

h) cutting the films to produce a multi-compartment pouch

The first and second forming machines are selected based on theirsuitability to perform the above process. The first forming machine ispreferably a horizontal forming machine. The second forming machine ispreferably a rotary drum forming machine, preferably located above thefirst forming machine.

It will be understood moreover that by the use of appropriate feedstations, it is possible to manufacture multi-compartment pouchesincorporating a number of different or distinctive compositions and/ordifferent or distinctive liquid, gel or paste compositions.

Solid Form.

As noted previously, the laundry care compositions may be in a solidform. Suitable solid forms include tablets and particulate forms, forexample, granular particles, flakes or sheets. Various techniques forforming detergent compositions in such solid forms are well known in theart and may be used herein. In one aspect, for example when thecomposition is in the form of a granular particle, the leuco colorant isprovided in particulate form, optionally including additional but notall components of the laundry detergent composition. The colorantparticulate is combined with one or more additional particulatescontaining a balance of components of the laundry detergent composition.Further, the colorant, optionally including additional but not allcomponents of the laundry detergent composition, may be provided in anencapsulated form, and the shading dye encapsulate is combined withparticulates containing a substantial balance of components of thelaundry detergent composition. Suitable pre-mix particles forincorporation of dyes/benefit agents into laundry care compositions ofthe invention are described for example in WO2010/084039, WO2007/039042,WO2010/022775, WO2009/132870, WO2009/087033, WO2007/006357,WO2007/039042, WO2007/096052, WO2011/020991, WO2006/053598,WO2003/018740 and WO2003/018738.

Method of Use.

The compositions of this invention, prepared as hereinbefore described,can be used to form aqueous washing/treatment solutions for use in thelaundering/treatment of fabrics. Generally, an effective amount of suchcompositions is added to water, for example in a conventional fabricautomatic washing machine, to form such aqueous laundering solutions.The aqueous washing solution so formed is then contacted, typicallyunder agitation, with the fabrics to be laundered/treated therewith. Aneffective amount of the liquid detergent compositions herein added towater to form aqueous laundering solutions can comprise amountssufficient to form from about 500 to 7,000 ppm of composition in aqueouswashing solution, or from about 1,000 to 3,000 ppm of the detergentcompositions herein will be provided in aqueous washing solution.

Typically, the wash liquor is formed by contacting the laundry carecomposition with wash water in such an amount so that the concentrationof the laundry care composition in the wash liquor is from above 0 g/lto 5 g/l, or from 1 g/l, and to 4.5 g/l, or to 4.0 g/l, or to 3.5 g/l,or to 3.0 g/l, or to 2.5 g/l, or even to 2.0 g/l, or even to 1.5 g/l.The method of laundering fabric or textile may be carried out in atop-loading or front-loading automatic washing machine, or can be usedin a hand-wash laundry application. In these applications, the washliquor formed and concentration of laundry detergent composition in thewash liquor is that of the main wash cycle. Any input of water duringany optional rinsing step(s) is not included when determining the volumeof the wash liquor.

The wash liquor may comprise 40 liters or less of water, or 30 liters orless, or 20 liters or less, or 10 liters or less, or 8 liters or less,or even 6 liters or less of water. The wash liquor may comprise fromabove 0 to 15 liters, or from 2 liters, and to 12 liters, or even to 8liters of water. Typically from 0.01 kg to 2 kg of fabric per liter ofwash liquor is dosed into said wash liquor. Typically from 0.01 kg, orfrom 0.05 kg, or from 0.07 kg, or from 0.10 kg, or from 0.15 kg, or from0.20 kg, or from 0.25 kg fabric per liter of wash liquor is dosed intosaid wash liquor. Optionally, 50 g or less, or 45 g or less, or 40 g orless, or 35 g or less, or 30 g or less, or 25 g or less, or 20 g orless, or even 15 g or less, or even 10 g or less of the composition iscontacted to water to form the wash liquor. Such compositions aretypically employed at concentrations of from about 500 ppm to about15,000 ppm in solution. When the wash solvent is water, the watertemperature typically ranges from about 5° C. to about 90° C. and, whenthe situs comprises a fabric, the water to fabric ratio is typicallyfrom about 1:1 to about 30:1. Typically the wash liquor comprising thelaundry care composition of the invention has a pH of from 3 to 11.5.

In one aspect, such method comprises the steps of optionally washingand/or rinsing said surface or fabric, contacting said surface or fabricwith any composition disclosed in this specification then optionallywashing and/or rinsing said surface or fabric is disclosed, with anoptional drying step.

Drying of such surfaces or fabrics may be accomplished by any one of thecommon means employed either in domestic or industrial settings. Thefabric may comprise any fabric capable of being laundered in normalconsumer or institutional use conditions, and the invention isparticularly suitable for synthetic textiles such as polyester and nylonand especially for treatment of mixed fabrics and/or fibers comprisingsynthetic and cellulosic fabrics and/or fibers. As examples of syntheticfabrics are polyester, nylon, these may be present in mixtures withcellulosic fibers, for example, polycotton fabrics. The solutiontypically has a pH of from 7 to 11, more usually 8 to 10.5. Thecompositions are typically employed at concentrations from 500 ppm to5,000 ppm in solution. The water temperatures typically range from about5° C. to about 90° C. The water to fabric ratio is typically from about1:1 to about 30:1.

The laundry care compositions of the present invention may also includeany number of additional optional ingredients. These includeconventional laundry detergent composition components such asnon-tinting dyes, detersive builders, enzymes, enzyme stabilizers (suchas propylene glycol, boric acid and/or borax), suds suppressors, soilsuspending agents, soil release agents, other fabric care benefitagents, pH adjusting agents, chelating agents, smectite clays, solvents,hydrotropes and phase stabilizers, structuring agents, dye transferinhibiting agents, opacifying agents, optical brighteners, perfumes andcoloring agents. The various optional detergent composition ingredients,if present in the compositions herein, should be utilized atconcentrations conventionally employed to bring about their desiredcontribution to the composition or the laundering operation. Frequently,the total amount of such optional detergent composition ingredients canrange from about 0.01% to about 50%, more preferably from about 0.1% toabout 30%, by weight of the composition.

Thus, the leuco colorant of the present invention may be added totextile substrates using a variety of application techniques. Forapplication to textile substrates, the bluing agent is preferablyincluded as an additive in a laundry care composition. Thus, applicationto the textile substrate actually occurs when a consumer adds a laundrycare composition, such as detergent, to a washing machine. Similarly,rinse added fabric softener compositions are typically added in therinse cycle, which is after the detergent solution has been used andreplaced with the rinsing solution in typical laundering processes. Forapplication to paper substrates, the bluing agent may be added to thepaper pulp mixture prior to formation of the final paper product.

The leuco colorant compounds of this invention, prepared as hereinbeforedescribed, can be used to form laundry care compositions and otherhousehold cleaning compositions, including without limitation, aqueouswashing solutions for use in the laundering of fabrics, solid surfacecleaners, dish and skin cleaners, and shampoos. As one example, aneffective amount of a laundry care composition containing the inventivecolorant may be added to water, preferably in a conventional fabriclaundering automatic washing machine, to form an aqueous launderingsolution. The aqueous washing solution so formed is then contacted,preferably under agitation, with the fabrics to be laundered therewith.

It is also contemplated to be within the scope of the present inventionthat the leuco colorant compounds described herein may be useful forcoloring articles such as foam (e.g. polyurethane foam) andthermoplastic materials. For example, the present invention alsoencompasses an article comprising at least one surfactant and at leastone leuco colorant. In this regard, the surfactant may be selected fromany already described herein. However, other surfactants may be suitablefor use as well, such as silicon surfactants that are commonly used inpolyurethane materials. Typically, commercially available organo siliconsurfactants and/or emulsifiers are polymers which contain a plurality ofsilicon atoms forming the hydrophobic portion of the polymer and a longchain hydrophilic group, for example, a polyoxyalkylene ether group. Themore common organo silicon surfactant/emulsifiers contain a siloxanegroup. Such compounds are described in detail in U.S. Pat. No.3,884,848, which is herein incorporated by reference. Any surfactantsdescribed in this specification, either alone or in combination, may besuitable for use in the present invention. Selection of suitablesurfactants will generally depend upon the end-use application of thecomposition and/or article containing the leuco colorant.

Additionally, it is noted that the leuco colorants may be modified asnecessary in order to provide stability of the colorant when added as aningredient to other chemical compositions. For example, certain groupsattached to the chromophore of the colorant composition may be modifiedto provide equilibrium and stability of the colorant in the desiredend-use application. For instance, the ionic strength of the end-useapplication, such as a chemical composition, may affect the equilibriumof the colorant. Accordingly, modifications to the colorant may be madeto polymer chains and other groups attached to the colorant. Insurfactant-containing compositions, it may be desirable to modify thecolorant so that it has the same or very similar surface energy and/orHLB properties as the surfactant-containing composition.

The leuco colorants of the present invention may be used for shading oftextile substrates (such as white garments) and/or paper products. Blueand/or violet are typically preferred shades and therefore preferredcolorants or mixtures of colorants that provide blue and/or violetshades are desirable. The leuco colorants of the present inventionprovide these desirable blue and/or violet shades. In this regard, theleuco colorants give a blue or violet color to white substrates with ahue angle of 240 to 345, or even a hue angle of 260 to 320, or even ahue angle of 270 to 300. For testing purposes, the white substrate maybe a white textile substrate that has been bleached and mercerized, suchas a woven cotton sheet.

EXAMPLES

The following examples are provided to further illustrate the leucocolorants of the present invention; however, they are not to beconstrued as limiting the invention as defined in the claims appendedhereto. In fact, it will be apparent to those skilled in the art thatvarious modifications and variations can be made in this inventionwithout departing from the scope or spirit of the invention. All partsand percents given in these examples are by weight unless otherwiseindicated.

Color Synthesis:

Example leuco colorant EX1 in Tables 1A and 1B, Leuco crystal violet,was purchased from Aldrich. Examples EX2-EX10 in Tables 1A and 1B wereprepared following the general process described below.

A four neck flask was equipped with an overhead stirrer, a condenser, atemperature controller, a heating mantle and a Nitrogen inlet. Then,about 2 moles of alkoxylated aniline (N-methyl aniline for EX9, and2-(phenyl amino) ethanol for EX 10) was added to the flask and heated toabout 65-71° C. During heating, about 1 mole of dimethylaminobenzaldehyde and catalytic amount (about 0.4 mole in this case) ureapre-dissolved in small amount of water were added. After the abovechemicals were mixed, about 1.2 mole of hydrochloric acid (in form ofMuriatic acid) was added drop wise to control the temperature below90-100° C. After the addition of hydrochloric acid, the reaction wasstirred at 95-100° C. for about 7 hours.

An exemplary synthesis route is shown below:

Synthetic Example 2: Synthesis of Leuco Crystal Violet 10 EO (LCV 10EO)

Synthesis and structure of Leuco Crystal Violet 10 EO can be describedas following:

Multiple methods can be used to retrieve the leuco colorant synthesizedby the above process. One of the methods was to first neutralize thereaction product to pH about 9; then remove the water by rot-yap. Theviscous material was diluted with an organic solvent such as isopropanoland filtered to remove the inorganic salts. The organic solvent wasevaporated and the final product was obtained.

Synthetic Example 6: Synthesis of Leuco Crystal Violet 4 EO (LCV 4EO)

In one embodiment, LCV 4EO was synthesized by following process: In a250 mL flask equipped with a mechanical stirrer, thermocouple, andsub-surface nitrogen inlet, 15 grams of p-dimethylaminobenzaldehyde,36.2 grams aniline 2EO, 18 grams of water and 3.5 grams of urea wascharged. Then 35 grams of concentrated hydrochloric acid (˜37%) wasslowly added to the reaction and the exotherm was controlled to about50° C. After the addition of the hydrochloric acid, the reaction washeated to 90° C. for about 6 hours. Then the reaction was cooled down toabout 55° C. and 100 gram of water was added. The solution was thenadded to 600 mL of 5% sodium bicarbonate solution under stir. Theproduct precipitated out and was collected and dried. The product wasfurther purified by dissolving in ethyl acetate and washed with water toremove the oxidized dye. The ethyl acetate was then evaporated to obtaina light green solid. The molar attenuation coefficient at 590 nm was 45liter/g/cm in methanol, in comparison of 87000 liter/mol/cm for thefully developed colorant.

EX 11 was prepared by reduction of pararosaniline hydrochloride.Specifically, 115.18 grams of pararosaniline hydrochloride, 200 mL ofmethanol, 11.1 mL of 5N sodium hydroxide, and 1.86 grams sodiumborohydride were stirred at room temperature for about 1 hour. Then thepH was adjusted to 7-9 and the product precipitated out. Filtering wasdone to collect the product.

COMPARATIVE EXAMPLES Comparative Example 1

Comparative Example 1 (CEX1) with the following structure was preparedby the process below.

A 500 mL four neck flask was equipped with an overhead stirrer, acondenser, a temperature controller, a heating mantle and a Nitrogeninlet. Then, 198 g of aniline 55 (aniline alkoxylated with 5 ethyleneoxide and 5 propylene oxide) was added to the flask and heated to about65-71° C. During heating, 24.5 g of dimethylamino benzaldehyde and 5.6 gurea (pre-dissolved 5.6 mL water) were added. After the above chemicalswere mixed, about 33.14 g of muriatic acid was added drop wise tocontrol the temperature below 90-100° C. After the addition, thereaction was stirred at 95-100° C. for about 7 hours.

After holding, 0.36 g of ammonium meta vanadate was added. Then amixture of 32.1 g 30% hydrogen peroxide and 29.1 g water was added dropwise into the reaction. The addition took about 2-3 hours in order tocontrol the temperature below 105° C. After addition, the reaction wasstirred for additional 15 minutes and about 11 gram of water was addedtill the mixture had a color value of about 48. (Color value is definedas the theoretical absorbance at the maximum absorbance wavelength ofthe 1 g/L solution of the colorant with 1 cm light path length).

Comparative Example 2

Comparative Example 2 (CEX2) with the following structure (crystalviolet lactone 10 EO) was synthesized following the procedure describedin U.S. Pat. Nos. 7,544,216; 7,597,723 and 7,637,963.

Detergent Formulations:

Several commercially available powdered detergents were utilized fortesting purposes in order to illustrate the advantages of the inventiveleuco colorants of the present invention. The powdered detergents arelisted below.

-   -   AATCC 1193 Standard Reference Detergent without optical        brightener (OB), available from available from AATCC        (Association of Textile, Apparel and Materials Professionals),        Research Triangle Park, N.C., USA. Ingredients include linear        alkylbenzene sulfonate sodium salt (C11, 8 LAS), sodium        aluminosilicate solids, sodium carbonate, sodium silicate solids        (SiO₂/Na₂O=1,6), sodium sulfate, polyethylene glycol, sodium        polyacrylate, silicone (suds suppressor), moisture,        miscellaneous (unreacted in surfactant stocks).    -   Tide® Ultra Free and Gentle, available from The Procter & Gamble        Company of Cincinnati, Ohio. Detergent ingredients include        sodium carbonate (removes water hardness), sodium        aluminosilicate (removes water hardness), alkyl sulfate        (surfactant), sodium sulfate (processing aid), linear        alkylbenzene sulfonate (surfactant), water (processing aid),        sodium polyacrylate (dispersant), silicate (processing aid),        ethoxylate (surfactant), sodium percarbonate (oxygen bleach),        polyethylene glycol 4000 (stabilizer), protease (enzyme; stain        remover), disodium diaminostilbene disulfonate (whitening        agent), silicone (suds suppressor), and cellulase (enzyme; stain        remover).    -   Persil® Power Gold Plus with brightness, available from Henkel        of Dusseldorf, Germany. Ingredients include sodium sulfate;        sodium carbonate; benzenesulfonic acid C10-13 alkyl derivatives        sodium salt; silicic acid sodium salt; sodium carbonate        peroxide; sodium polyacrylate; fatty alcohol ethoxylate C12-18        7EO; water; carboxymethylcellulose, Na salt; TAED; tetrasodium        etidronate; starch; perfume;        4,4′-bis[(4-anilino-6-morpholino-1,3,5-triazine-2-YL)amino]stilbene-2,2′-disulfonate        de disodium; sodium hydroxide; di-me        methyl(2-phenylpropyl)siloxane; colorant; protease; linalool;        amylase; mannanase-1,4,endo-β-; cellulase; and formaldehyde.    -   Vanish detergent, available from Reckitt Benckiser of Berkshire,        United Kingdom. Ingredients include sodium percarbonate, sodium        carbonate, sodium sulphate, tetraacetylethylenediamine (TAED),        disodium disilicate, water, sodium dodecylbenzenesulfonate        (linear alkyl benzene sulfonate), pareth-5, zeolite, protease,        perfume, lipase, and amylase.    -   ROMA detergent, available from La Corona Soap Factory in Mexico.        Ingredients include linear anionic surfactant (cleaning agent),        aluminosilicates and silicate (water softener),        carboxymethylcellulose (soil suspending agent), fabric        brightener, and perfume.    -   Mr. White detergent, available from Vaishnavi Kosmetics Ind Pvt.        Ltd. of Himachal Pradesh, India.    -   RIN detergent, available from Hindustan Unilever Ltd of Mumbai,        India.    -   Liby detergent, available from Guangzhou Lily Enterprise Group        Co., Ltd. Of Guangdong Province, China. Ingredients include        stain separation component, compound surfactants, phosphate-free        water softener, enzyme, cleaning performance particle, oxy-clean        component with brightening and antibacterial, and perfume.        Test Methods and Results:        Calculation of Whiteness: CIELab b* and Ganz and CIE Whiteness        Index

Whiteness Index (“WI”) is a qualifying assessment of color that iscalculated by a formula which includes three components of colormeasurement—hue, saturation, and lightness—which is then indexed to astandard white value. Several whiteness formulas can be used to measurewhiteness on cellulose based substrates. Two common formulas are theGanz Whiteness Index and CIE Whiteness. Ganz Whiteness Index isexpressed by the formula: WI=(D*Y)+(P*x)+(Q*y)+C, where Y, x and y arecolorimetric values and D, P, Q and C are formula parameters. CIEWhiteness is expressed by the formula: WI=Y−(800*x)−(1700*y)+813.7,where Y, x and y are colorimetric values. Higher positive Ganz WI valuesindicate that more blueing, or whitening effect, is exhibited by thetreated cellulose based substrate. Further information is available inthe publication of Rolf Griesser, Ciba-Geigy Ltd, “Whiteness and Tint”,June 1993.

The surface color of an article may be quantified using a series ofmeasurements—L*, a*, and b*—generated by measuring the samples using aspectrophotometer. The equipment used for this test was a Gretag MacbethColor Eye 7000A spectrophotometer. The software program used was “Colorimatch.” “L” is a measure of the amount of white or black in a sample;higher “L” values indicate a lighter colored sample. A measure of theamount of red or green in a sample is determined by “a*” values. Ameasure of the amount of blue or yellow in a sample is determined by“b*” values; lower (more negative) b* values indicate more blue on asample.

Yet another measurement of the relative color of a substrate is DE CMC.DE CMC is a measure of the overall color difference for all uniformcolor spaces, where DE CMC represents the magnitude of differencebetween a color and a reference. The Gretag Macbeth Color Eye 7000ASpectrophotometer calculates DE CMC values based on wavelength andreflectance data for each sample.

Several leuco colorants of the present invention and several comparativeexamples were prepared and tested for bluing efficiency. Lower (morenegative) CIELab b* values indicate that more bluing, or whiteningeffect, is exhibited by the treated cotton swatch.

Comparison of Inventive Example EX4 and Comparative Example CEX1

To illustrate the invention, two detergent compositions were preparedand compared. One detergent composition contained Inventive Example 4(EX4; Example 4 in Tables 1A and 1B), and the other containedComparative Example CEX1. EX4 and CEX1 had the same polymer chains, butEX4 was a leuco colorant and CEX1 was a conventional colorant. The twocolorants were separately blended with a low pH detergent (in this case,Tide® Free and Gentle detergent). The amounts of the colorants (400 ppmfor EX4 and 200 ppm for CEX1) were determined so that the detergents hadabout the same hueing effect. The appearance (in terms of The CIE L*,a*, and b* values) of both detergents were read and compared in Table 2.

The bluing effect of the detergents containing both EX4 and CEX1 wascompared by the following test. In a 1 liter beaker, 500 mL of tapwater, 0.5 gram of the detergent premixed with the colorants were mixed.Then 6 pieces of bleached cotton t-shirt fabric (purchased fromTestfabrics, Inc., style number 437W-60, cut to 6″ by 6″ size) wereadded to the wash water and washed with tergotometer at room temperaturefor 15 minutes. The fabric/water ratio is about 40 gram/liter. Afterwash, the fabric samples were rinsed by hand with 500 mL tap water twiceand then dried in a dryer for 1 hour. The CIE L*, a*, and b* values wereread with a color eye spectrophotometer for the first wash effect. Thenthe dried cottons were washed and rinsed two more times as describedabove, and finally dried again in a drier. The CIE L*, a*, and b* valueswere read with a color eye spectrophotometer for three wash effects.

The delta b* values of the samples washed are reported in the Table 2below. The delta b* value was obtained by subtraction with the b* valueof the same kind of fabrics washed with the same procedure and the samedetergent but containing no hueing dyes.

In Table 2, the application example 2 containing leuco colorant (EX4)has light color (L*=94.5) comparable with the base detergent(application example 1, L*=95.3), and demonstrates good hueing effect inboth first wash and three-wash. The application example with CEX1,delivers about same bluing effect but has much darker color (L*=28.0).

TABLE 2 Loading of Appli- hueing dye First- Three- cation Hueing inL*/a*/b* of wash wash Example dye detergent detergent delta b* delta b*1 None 0 95.3/−2.9/9.4 0 0 2 EX4 400 ppm 94.9/−3.2/9.7 −0.5 −0.5 3 CEX1200 ppm 28.0/61.4/−83.1 −0.3 −0.4

Comparison of Inventive Example EX2 and Comparative Example CEX2

The bluing effect of the EX2 and CEX2 was compared by the followingtest. The test procedure is described below:

In a 1 liter beaker, 500 mL of tap water, 0.5 gram of Tide® free andgentle liquid detergent, and the leuco dye to be tested (loading of theleuco dye was included in Table 3 below) was mixed. Then 6 pieces ofbleached cotton t-shirt fabric (purchased from Testfabrics, Inc., stylenumber 437W-60, cut to 6″ by 6″ size) were added to the wash water andwashed with tergotometer at room temperature for 15 minutes. Thefabric/water ratio was about 40 gram/liter. After wash, the fabricsamples were rinsed by hand with 500 mL tap water twice and then driedin a dryer for 1 hour. The dried samples were then washed and rinsed twomore times as described above, and finally dried again in a drier. TheCIE L*, a*, and b* values were read with a color eye spectrophotometer.

The delta b* values of the cotton washed with different leuco hueingdyes are reported in the Table 3 below. The delta b* value was obtainedby subtraction with the b* value of the same kind of fabrics washed withthe same procedure and the same detergent but containing no leuco hueingdyes as described above. The example of this invention (EX2) is moreeffective in hueing fabrics than the comparative example CEX2 even atlower loading (1 ppm vs. 2 ppm).

TABLE 3 Concentration of Application Hueing Dye in wash Three-washExample Hueing dye water delta b* 4 EX2 1 ppm −0.9 5 CEX2 2 ppm 0.1

Bluing Effect of the Inventive Examples in Low pH Detergent

The bluing effect of the inventive examples listed in Tables 1A and 1Bwas tested following the procedure described below:

In a 1 liter beaker, 500 mL of tap water, 0.5 gram of detergent (Tide®free and gentle liquid detergent or AATCC standard liquid laundrydetergent, both have a low pH about 8-9), and the leuco dye to be tested(loading of the leuco dye was included in Table 4 below) were mixed. Theleuco dye can be introduce into the wash water by either 1) premixingwith the detergent or 2) pre-dissolving in about 1 mL of organic solventand then add directly into the wash water. Six pieces of bleached cottont-shirt fabric (purchased from Testfabrics, Inc., style number 437W-60,cut to 6″ by 6″ size) were added to the wash water and washed withtergotometer at room temperature for 15 minutes. The fabric/water ratiowas about 40 gram/liter. After wash, the fabric samples were rinsed byhand with 500 mL tap water twice and then dried in a dryer for 1 hour.The CIE L*, a*, and b* values were read with a color eyespectrophotometer.

The delta b* values of the cotton washed with different leuco hueingdyes are reported in the Table 4 below. The delta b* values wereobtained by subtraction with the b* value of the same kind of fabricswashed with no hueing dyes following the same procedure described above.

TABLE 4 Application Leuco Detergent Concentration of hueing Examplecolorants used dye in wash water delta b* 6 EX1 Tide ® 1 ppm −2.6 7 EX2Tide ® 1 ppm −0.9 8 EX3 Tide ® 5 ppm −0.9 9 EX4 Tide ® 1 ppm −0.7 10 EX4Tide ® 0.4 ppm   −0.3 11 EX5 AATCC 1 ppm −0.8 12 EX6 AATCC 1 ppm −2.4 13EX7 AATCC 1 ppm −1.6 14 EX8 AATCC 1 ppm −1.2

Bluing Effect of the Inventive Examples in High pH Detergent

The leuco colorants EX2 and EX4 were mixed with a high pH detergent(ALL® detergent, pH is about 12.4). The amount of the colorant indetergent was chosen according to the concentration of colorant in thewash water as listed in Table 5. Then, in a 1 liter beaker, 500 mL oftap water, 0.5 gram of the detergent was mixed. Then 6 pieces ofbleached cotton t-shirt fabric (purchased from Testfabrics, Inc., stylenumber 437W-60, cut to 6″ by 6″ size) were added to the wash water andwashed with tergotometer at room temperature for 15 minutes. Thefabric/water ratio was about 40 gram/liter. After wash, the fabricsamples were rinsed by hand with 500 mL tap water twice and then driedin a dryer for 1 hour. The CIE L*, a*, and b* values were read with acolor eye spectrophotometer.

The delta b* value of the cotton washed with different leuco hueing dyesare reported in the Table 5 below. The delta b* value were obtained bysubtraction with the b* value of the same kind of fabrics washed with nohueing dyes following the same procedure described above.

TABLE 5 Concentration of Application Hueing Dye in wash Example LeucoColorant water delta b* 15 EX2   1 ppm −0.7 16 EX4 0.5 ppm −0.4

Storage Stability of the Inventive Examples in Low pH Detergent

400 ppm of EX4 was mixed with Tide® Free and Gentle liquid detergent.Then the detergent was aged at 1) room temperature and 2) 50° C. for 4weeks. The CIE L*, a*, and b* values of the detergent containing theleuco colorant were measured and compared before and after storage. Thehueing efficiency of the detergent was also tested and compare followingthe same washing protocol as the application example 6-14.

In addition to the leuco colorant, other additives can be added to thedetergent formulation to either promote the color development duringwash and/or inhibit the color formation during storage. These additivesinclude, but are not limited to, antioxidant, reducing agent, oxidizer,oxidizing catalyst, and combinations thereof. Suitable antioxidantsinclude, but are not limited to, alkylated phenol (such as BHT, Irganox®1135, Irganox® 1076, Irganox® 1010, Irganox® 1330, and Irganox® 1035;Irganox® products commercially available from BASF), aromatic amine andits derivatives (such as Irganox® 5057), α-, β-, γ-, δ-tocopherol,ethoxyquine, 2,2,4-trimethyl-1,2-dihydroquinoline, 2,6-di-tert-butylhydroquinone, tert-butyl-hydroxy anisole, lignosulphonic acid and saltsthereof, 6-hydroxy-2,5,7,8-tetra-methylchroman-2-carboxylic acid(Trolox™), 1,2-benzisothiazoline-3-one (Proxel GXL™), a benzofuran orbenzopyran derivative (such as Irganox® HP136), AOX-1 commercialized byMilliken & Company of Spartanburg, S.C., USA, tocopherol sorbate,butylated hydroxy benzoic acid and its salts, gallic acid and its alkylesters, uric acid and its salts and alkyl esters, sorbic acid and itssalts, dihydroxy fumaric acid and its salts, hindered amines andmixtures thereof.

The detergent formulation and hue data before and after storage wascompared in Table 6.

TABLE 6 Loading Loading of of L*/a*/b* L*/a*/b* L*/a*/b* ApplicationAdditive Additive before after storage after storage Example 1^(a) 2^(b)storage 25° C. 50° C. 17 0 0 93.6/−3.5/8.2 92.9/−3.8/6.7 88.4/−5.2/1.218 800 ppm 0 91.9/−4.2/8.3 91.7/−4.2/8.1 90.8/−4.5/8.2 19 0 800 ppm92.2/−3.5/7.1 93.6/−3.5/5.0 89.3/−4.6/−2.7 20 400 ppm 400 ppm92.4/−3.4/6.7 94.2/−3.4/6.2 91.8/−4.1/3.0 ^(a)additive 1 is3,5-Di-tert-butyl-4-hydroxybenzenepropanoic acid (CAS 20170-32-5).^(b)additive 2 is sodium dithionite (CAS 7775-14-6).

1000 ppm of EX2 was mixed with Tide® Free and Gentle liquid detergentwith/without other additives. The storage stability was tested andsummarized in the Table 7 below.

TABLE 7 Loading Loading of of L*/a*/b* L*/a*/b* After ApplicationAdditive Additive before L*/a*/b* After storage Example 1^(a) 2^(b)storage storage 25° C. 50° C. 21 0 0 91.0/−5.2/6.5 85.1/−7.5/6.272.8/−9.8/−6.9 22 2000 ppm 0 91.1/−5.5/7.7 88.3/−7.2/ 77.5/−8.5/4.4 15.223 1000 ppm 0 91.0/−5.3/7.2 88.3/−7.1/ 77.8/−8.8/2.7 13.1 24 0 2000 ppm95.7/−4.3/ 92.3/−4.8/4.3 77.2/−6.2/−20 10.3 25 0 1000 ppm 91.8/−5.2/6.089.9/−5.3/0.7 72.8/−6/−25 ^(a)additive 1 is3,5-Di-tert-butyl-4-hydroxybenzenepropanoic acid (CAS 20170-32-5).^(b)additive 2 is sodium dithionite (CAS 7775-14-6).

The delta b* values of the cotton washed with the application example18, 21, and 23 before and after aging at 50° C. for 4 weeks werecompared in Table 8 below. The detergents maintained the hueingefficiency after storage.

TABLE 8 Application delta b* delta b* after Example before aging aging18 −0.5 −0.3 21 −0.7 −0.7 23 −0.8 −0.6

Storage Stability of the Inventive Examples in High pH Detergent

1000 ppm of EX2 was mixed with ALL® detergent. Then the detergent wasaged at 1) room temperature and 2) 50° C. for 4 week. The CIE L*, a*,and b* values of the detergent containing the leuco colorant weremeasured and compared before and after storage. The hueing efficiency ofthe detergents were also tested and compare following the same washingprotocol as the application example 15 and 16.

The detergent formulation and L*, a*, and b* values before and afterstorage were compared in Table 9.

TABLE 9 L*/a*/b* Application before L*/a*/b* After L*/a*/b* AfterExample storage storage 25° C. storage 50° C. 26 95.4/−4.4/8.296.0/−4.2/9.2 96.0/−4.3/9.2

The delta b* values of the cotton washed with the application example 23and after aging at 50° C. for 4 weeks were compared in Table 10 below.The detergent maintained its hueing efficiency after storage.

TABLE 10 Application delta b* delta b* after Example before aging aging26 −0.7 −0.6

Bluing Effect of the Inventive Examples in Powder Detergent

The powder detergents containing the leuco dye were prepared by mixingthe leuco dye with a variety of powder detergents as listed in Table 11.Then, in a 1 liter beaker, 500 mL of tap water and 0.5 gram of powderlaundry detergent containing the leuco dye to be tested were mixed (washwater concentration of the leuco dye is included in Table 11 below). Sixpieces of bleached cotton t-Shirt fabric (purchased from Testfabrics,Inc., style number 437W-60, cut to 6″ by 6″ size) were added to the washwater and washed with tergotometer at room temperature for 15 minutes.The fabric/water ratio was about 40 gram/liter. After wash, the fabricsamples were rinsed by hand with 500 mL tap water twice and then driedin a dryer for 1 hour. The CIE L*, a*, and b* values were read with acolor eye spectrophotometer.

The delta b* values for cotton washed with a single leuco hueing dye(EX4) premixed with many different powdered laundry detergents arereported in the Table 11 below. The delta b* values were obtained bysubtracting the b* value recorded when the same kind of fabrics werewashed with detergent only (no hueing dye present), following the sameprocedure described above.

TABLE 11 Powdered Application Leuco Detergent Concentration of hueingExample colorant used dye in wash water delta b* 27 EX4 AATCC 1 ppm−1.39 Detergent w/o OB 28 EX4 Tide ® 1 ppm −0.53 Free & Gentle 29 EX4Persil ® 1 ppm −1.33 Power 30 EX4 Vanish 1 ppm −0.29 31 EX4 ROMA 1 ppm−1.1 32 EX4 Mr. White 1 ppm −2.02 33 EX4 RIN 1 ppm −0.6 34 EX4 LIBY 1ppm −1.12

Bluing Effect of the Inventive Examples in Different Water Source

Tap water is often treated with chlorine species to disinfect. Commonlyused disinfecting agents include, but are not limited to, chlorine,chlorine dioxide, chloramine, and combinations thereof. The method ofmeasuring the chlorine level in water is well known to those skilled inthe art. One method uses a chlorine kit and colorimeter commercializedby Hach. Since disinfecting agents are oxidizing in nature, differentwater sources will have an influence on the bluing efficacy of the leucocompound. The effect of chlorine species on bluing is dependent on theformulation of the detergent. Some detergent formulations contain a“chlorine scavenger” which acts to deactivate the active chlorine in thetap water. Other additives in detergent formulations, such as theanti-oxidant and reducing agent, may also have effect on the chlorinespecies.

Table 12 lists some application examples using leuco colorant in waterwith different chlorine source and concentration. The total chlorinelevel was measured using Hach total chlorine kit and colorimeter.

In a 1 liter beaker, 500 mL of water, 0.5 gram of detergent (Tide® Freeand Gentle liquid detergent, pH about 8-9), and the leuco dye to betested (loading of the leuco dye was included in Table 12 below) weremixed. The leuco dye can be introduced into the wash water by either 1)premixing with the detergent or 2) pre-dissolving in about 1 mL oforganic solvent and then add directly into the wash water. Six pieces ofbleached cotton t-shirt fabric (purchased from Testfabrics, Inc., stylenumber 437W-60, cut to 6″ by 6″ size) were added to the wash water andwashed with tergotometer at room temperature for 15 minutes. Thefabric/water ratio was about 40 gram/liter. After wash, the fabricsamples were rinsed by hand with 500 mL testing water twice and thendried in a dryer for 1 hour. The CIE L*, a*, and b* values were readwith a color eye spectrophotometer.

The delta b* values of the cotton washed with different leuco hueingdyes are reported in Table 12 below. The delta b* values were obtainedby subtraction with the b* value of the same kind of fabrics washed withno hueing dyes following the same procedure described above.

TABLE 12 Total Hueing dye Application Leuco Chlorine Chlorine in washdelta Example colorants level species water b* 35 EX6 0 — 1 ppm −0.5 36EX6 2.82 ppm Chloramine 1 ppm −1.1 37 EX6 1.16 ppm Chlorine 1 ppm −1.038 EX7 0 — 1 ppm −0.5 39 EX2   1.58 Chlorine 0.2 ppm   −1.6 and Chlorinedioxide 40 EX2 0 — 0.2 ppm   0 41 EX2 2.82 ppm Chloramine 0.2 ppm   −0.142 EX2 1.16 ppm Chlorine 0.2 ppm   −0.2 43 EX5 0 — 1 ppm −0.1 44 EX14 0— 1 ppm −0.3

While particular embodiments of the present invention have beenillustrated and described, it would be obvious to those skilled in theart that various other changes and modifications can be made withoutdeparting from the spirit and scope of the invention. It is thereforeintended to cover in the appended claims all such changes andmodifications that are within the scope of this invention.

We claim:
 1. A leuco triphenylmethane colorant according to thefollowing structure:


2. A leuco triphenylmethane colorant according to the followingstructure:


3. A leuco triphenylmethane colorant according to the followingstructure: